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By Stanislaus Skowronski

OVERPOLED copper, as commonly defined, is copper which has been excessively reduced during the poling period of the refining process. Owing to its porosity, such copper is unfit for commercial purposes. The cause of this phenomenon is undoubtedly the lack of oxides in the copper, yet this does not completely explain it. Refined copper of the same "pitch" and "set" varies considerably in oxygen contents, and analyses of overpoled bars also show similar wide differences; moreover, it is possible to melt copper in crucibles so as to obtain bars that are practically free from oxygen although they show a "tough pitch" and "level set" surface. Frederick Johnson advances the following theory: The regulation of the quantity of oxygen in copper is the keynote of all copper refining. It is the presence of a Well defined proportion of oxygen in the form of cuprous oxide, forming a copper-cuprous oxide eutectic, Which enables copper to be cast free from blowholes. It seems that When oxygen is present, other gases are less soluble in molten copper; When oxygen is absent, or is present in insufficient quantity, the copper dissolves other gases, such as hydrogen and carbon monoxide, Which are insoluble in the copper when solid, and, being rejected during the process of solidification, causes internal porosity and external ridges and excrescences.1 The "level set" of Wire bars, etc., is entirely the result of a compromise between the occluded gases and cuprous oxide. With excess of the former the metal would be "overpitch" and spongy, While an excess of the latter would result in the metal being "underpitch" and brittle.2 The result of the absorption and subsequent expulsion of reducing gases, carbon monoxide and hydrogen, and the effect of this action. on the overpoling of copper are in dispute; the literature on the subject is full of contradictory statements and will continue to be so until better analytical methods have been developed. Sulphur, however, is tangible. The refiner can see it in his button sample and consequently attributes to it any trouble that may happen during the melting of the copper.

Jan 3, 1918

By Charles Y. Clayton

The shank, to give good service, should not upset nor should it cause excessive wear on the various parts of the machine. To fulfill these requirements, the steel must have a certain hardness—that is, resistance to deformation. The hardness is expressed in conventional terms, as Brinell or scleroscope number. Before deciding on the hardness that is proper, several factors should be considered; the most important are: type of drill steel used (whether hollow or solid), length of steel, nature of ground, air pressure, and hardness of hammer or anvil block (usually 600 Brinell). These are not all, but they are the most cogent ones. Without doubt, it would be better to use a shank that is too soft than one that is too hard. Most satisfactory service will be obtained from shanks that are just hard enough to resist any tendency to upset. To express the proper hardness in terms of Brinell numbers would mean a great many tests over a long period of time, or a study of drill steels that are being used successfully in the various districts. To obtain some information along this line, the persons making this investigation requested, a number of companies to send to them drill shanks that had been given the usual treatment at that mine. The results of the hardness tests are given in Table 1. The hardness values given in Table 2 are those of shanks known to have been quenched in water and drawn. These results show that where water quenching and drawing are in vogue the hardness is rarely under 400 Brinell.

Jan 1, 1923

By Charles Y. Clayton

The shank, to give good service, should not upset nor should it cause excessive wear on the various parts of the machine. To fulfill these requirements, the steel must have a certain hardness—that is, resistance to deformation. The hardness is expressed in conventional terms, as Brinell or scleroscope number. Before deciding on the hardness that is proper, several factors should be considered; the most important are: type of drill steel used (whether hollow or solid), length of steel, nature of ground, air pressure, and hardness of hammer or anvil block (usually 600 Brinell). These are not all, but they are the most cogent ones. Without doubt, it would be better to use a shank that is too soft than one that is too hard. Most satisfactory service will be obtained from shanks that are just hard enough to resist any tendency to upset. To express the proper hardness in terms of Brinell numbers would mean a great many tests over a long period of time, or a study of drill steels that are being used successfully in the various districts. To obtain some information along this line, the persons making this investigation requested, a number of companies to send to them drill shanks that had been given the usual treatment at that mine. The results of the hardness tests are given in Table 1. The hardness values given in Table 2 are those of shanks known to have been quenched in water and drawn. These results show that where water quenching and drawing are in vogue the hardness is rarely under 400 Brinell.

Jan 1, 1923

By Marston G. Fleming

CRITICAL pH has been defined by Wark1 as that pH value below which a mineral will float and above which it will not float in solutions containing a given concentration of collector but free from other depressants or activators. - The relationship between mineral, collector concentration, and pH is expressed in the form of a critical pH curve determined by the captive bubble method and is generally regarded as being fundamental to the system involved. The mechanism of alkali depression is currently in dispute, two general theories having received authoritative support. The view expressed in Taggart's chemical theory of flotation2 is that in the presence of a critical concentration of hydroxyl ions, all the metal ions available at the surface of the mineral are present as anions of the form [M (OH)x]-y. The formation of the necessary metal xanthate is thus precluded and, furthermore, any metal xanthate coating previously formed, at a lower pH, will be dissolved. Gaudin3,4 and the Melbourne school under Ware hold that alkali depression is caused by the preferential adsorption of hydroxyl ions by the mineral surfaces. This paper describes an investigation of the mechanism of alkali depression in each of the three systems: cerussite-aqueous carbonate-xanthate, cerussite-xanthate, and galena-xanthate. Alkali Depression of Cerussite by Control of Carbonate Ion Concentration Wark and Cox6 have shown that in the presence of Na2CO3 a higher concentration of xanthate is required to effect bubble contact with a cerussite surface than in carbonate-free solutions. To examine this depression of cerussite by sodium carbonate, a series of captive bubble tests was carried out on cerussite specimens in solutions containing 100 mg per liter of potassium ethyl xanthate and varying concentrations of sodium carbonate. The pH was adjusted by the addition of dilute hydrochloric acid. For purposes of comparison a standard critical pH curve was determined for cerussite with potassium ethyl xanthate in solutions containing no added carbonate. In the latter case pH adjustment was made with sodium hydroxide. The experimental method employed in both series was broadly similar to that described by Wark and Cox;7-9 a number of refinements suggested by Sutherland10 were adopted, and the procedure was further developed and modified to suit the particular requirements of the investigation. The relationship between pH and the concentration of potassium ethyl xanthate necessary to induce bubble contact at cerussite surfaces is shown in Fig. 1. The relationship between pH and the concentra- [ ] tion of sodium carbonate necessary to prevent bubble contact at cerussite surfaces in the presence of 100 mg per liter of potassium ethyl xanthate is shown in Fig. 2. Comparison of the. two curves shows that at a collector concentration of 100 mg

Jan 1, 1952

By R. T. Webber, B. B. Owen

THE vapor phase deposition of molybdenum and tungsten from the hexacarbonyls has been thoroughly investigated by Lander and Germer1 and shown to yield well-bonded coatings on a variety of hot metallic surfaces. They also demonstrated that chromium coatings2.3 could be similarly deposited, but did not investigate this metal extensively. Recently,4 conditions have been described by which this compound can be prepared in quantities sufficient for laboratory scale plating experiments, and it is the purpose of the present communication to outline the results of preliminary experiments upon the plating of chromium from its carbonyl. APPARATUS AND TECHNIQUE The apparatus used in these experiments is shown in Fig I. At one end, connected by a short length of rubber tubing, is a Cenco Hypervac 20 pumping continuously. At the opposite end is a needle valve which allows a small stream of purified hydrogen to flow through the apparatus. Connected in series are a trap T1, maintained at the temperature of dry ice and acetone, the plating chamber, and two traps T2 and T3 containing crystals of the carbonyl. T2 is kept in a constant temperature bath (not shown), while T3 is at room temperature. Stopcock S6 allows the hydrogen flow to by-pass the carbonyl traps. A McLeod gauge is connected so that it can measure the pressure at the pump through Ss, or the pressure at the plating chamber through S9 and S6. The standard (12 liter) volume connected by S5 is used to determine the volume included by S4, S6, Se, S10, the needle valve and the McLeod gauge. Knowledge of this volume allows calibration of the flow of hydrogen. The apparatus* is built entirely of pyrex, except for the needle valve, the rubber connection to the Hypervac, and the cover of the plating chamber. The plating chamber is water-jacketed, with a large brass top allowing insertion of the specimen to be plated. Set into the brass top is a ground glass stopper through which thermocouple leads are sealed. The thermocouple wires (pure Pt, and 87 pct Pt-13 pct Rh) serve the double purpose of measuring the specimen temperature and suspending it in the chamber. Surrounding the chamber is the coil of an induction heater, H. The apparatus is designed to allow variation of the following conditions: I, the specimen temperature, from room temperature to about 1000°C, 2, the carbonyl vapor pressure, from 40 to 220 microns, and 3, the hydrogen flow. In several runs, 0.8 to 1.8 pct of hydrogen sulfide was introduced through a needle valve that replaced S4. The vapor pressure of the carbonyl is

Jan 1, 1948

By Alex Boozenny

The results of potential measurements between 1) a titaniurn electrode in NaCl-TiCl, melts and a graphite-cizlorine reference electrode and 2) a titanium electrode in NaC1-Nu "melts and a graphite-chlorine reference electrode show that the following relationship expresses the equilibrium relationship between the TiCl, and the dissolved metallic sodium concentrations, expressed in mole fraction units, in dilute NaCl welts at 850°C. The results of potential measurenments between a graphite electrode in NaCl-TiCl, melts that were saturated with TiCl, and a graphite-chlorine reference electrode, when combined with the standard free energy data given in literature, gave the following expression for the equilibrium relationship between the TiCl, and TiCl, concentrations, expressed in mole fraction units, in dilute NaCl melts at 850°C. These relationships are for melts in equilibrium with pure titanium. In impure systems, less sodiurn and more TiCI, can be copresent with a given concentration of TiCl,. AFTER 10 years of existence, the titanium metal industry still relies on the original Kroll and the sodium reduction processes for the only important means of converting titanium-bearing ores to titanium metal via production of titanium tetrachloride as an intermediate. Through years of modification and development these two processes have evolved to a point where any further major economic advances in the field of titanium metal production must be achieved through implementation of processes which are distinct departures from simple magnesium or sodium reduction of titanium tetrachloride. Concurrently with the refinement of the Kroll and sodium reduction processes, industries and government have sponsored research and development in the field of producing titanium by electrolysis of oxides,' carbides,' and halides3'4 in fused salt media. However, the incomplete understanding of the physical chemistry of fused salt systems has in many cases hindered the development of promising new titanium production processes to the point where they will have a clear advantage over the processes presently employed. Fortunately the volume of information on fused salt physical and electrochemistry is increasing at an accelerating pace. The first approaches tbward investigating the electrochemical behavior of fused salt systems have been the measurements of equilibrium potentials of metals immersed in melts containing their halides.' Some work on the kinetics of fused salt electrochemical processes has been reported.'09" Some descriptions of the structural composition of fused salt systems are also available. The work described herein is a continuation of the study of metal electrode potentials in fused salts. Specifically, this contribution to the growing store of fused salt chemistry information presents a description of the equilibrium relationships between the concentrations of titanium dichloride, titanium trichloride, and metallic sodium in fused sodium chloride. The investigation of the titanium dichloride-titanium trichloride equilibrium relationships is not completely new. Kellog and Krye and Melgren and opie15 have presented the results of chemical analysis of salts containing titanium chlorides. Flengas and lngrahaml' have published the results of an investigation of these equilibrium relationships obtained by measurement of electrode potentials in a fused NaCl-KC1 mixture. The investigation described herein differed from that of Flengas and Ingraham principally in the use of straight NaCl as the solvent in place of the more costly and more difficult to purify mixture. This investigation was conducted in three parts. First, the equilibrium potentials of titanium in sodium chloride containing known concentrations of titanium dichloride were measured. A graphite-chlorine electrode was employed as reference. Second, the equilibrium potentials of titanium immersed in sodium chloride containing known concentrations of elemental sodium were measured. Third, the equilibrium potentials of graphite immersed in titanium tetrachloride-saturated sodium chloride containing known concentrations of titanium trichloride were measured. The results of these three related investigations are presented in the above order. The results are combined with the thermodynamic properties of titanium chlorides and sodium chloride, obtained from literature, to give the titanium dichloride-titanium trichloride-elemental sodium equilibrium concentration relationships. In the test, whenever a melt contains titanium chlorides in predominantly divalent form, the melt

Jan 1, 1962

By N. K. Chen, R. B. Pond

IN the study of slip band* formation, there have been many examples to show that they do not always appear as lines traversing the entire crystal, but as segments whose ends seem to vanish in their path through the crystal. This characteristic appearance of slip bands has been witnessed under the optical microscope at various magnifications'-' and also under the electron microscope.' A typical example of this behavior seen with the optical microscope is shown in Fig. 1. However, the slip band studies were generally conducted on polished surfaces of single or poly-crystalline metals which had been previously deformed; i.e., the load was generally released so that the observation could be made. Any picture of slip bands so obtained can represent the surface phenomenon only in a static state of the strained material. The conditions prior to their formation cannot be definitely and clearly assigned. Thus, while a segmented slip band may suggest that slip is a growth process as supposed by the theory of the nucleation of slip,V he usual appearance of suddenly and fully developed slip bands around the crystal has generally been considered as a consequence of uniform shear of the entire slip plane akin to a cataclysmic process. Little clear-cut information is available with regard to the speed at which a slip band forms, its direction of motion, the geometry of its position with regard to its neighbors, and its dependence on orientation. A description is given in this paper of experimental apparatus by which the progressive formation of slip bands can be recorded while the specimen is undergoing deformation. Qualitative and quantitative data on the dynamic formation of slip bands will be presented with special interest concerning the propagation of slip bands, the spacing of slip bands, and their relations to strain hardening. Views on the formation of slip bands are discussed and a mechanism of the unit process involved in the formation of a slip band is proposed. Preparation of Specimens Single-crystal specimens of high purity aluminum (99.997 pct), 1/8 in. square in cross-section and 1% in. long in gage length, were made by the method of gradual solidification from the liquid state. Since no machining work could be introduced in preparation of crystals of such small size, a special mold was designed for casting them to final shape. The mold consisted of two, separate, high purity graphite blocks. Generally, 20 molds were packed together in one container so that 20 specimens could be obtained by one casting operation. This was desirable since it was possible by this method to obtain groups of crystals with similar orientations. The as-cast crystals were carefully clipped from the gate, etched, and homogenized for 24 hr at 600°C. They were then very gently polished using a 4/0 paper, re-etched, and finally electrolytically polished after the method previously described by Chen and Mathewson.6 The crystallographic orientations were determined using a back-reflection, Laue method. Tensile Testing and Photographic Method The tensile testing equipment for these tests was composed of a specially designed microtensile machine, microload cell and microclip gage with necessary appurtenances. The members of the microtensile machine consisted of three parts, as shown in Fig. 2. The chassis is equipped with an oil cylinder, A, and piston, the piston being part of the movable cross-head, B. Pressure in the oil cylinder is controlled and regulated by an external pneumatic-hydraulic cell, C, which is connected to the cylinder by a Vs in. high pressure copper tube. This cell is half filled with hydraulic oil and has a needle valve, D, on the oil exit side as well as a needle valve, E, on the gas inlet side. A quick-acting valve, F, as well as a pressure gage is provided for the gas side. The oil exits into the load piston on the microtensile machine. By connecting a tank of inert gas to the gas inlet, regulated pressures were provided over the oil so that the oil would leave the cell at a rate determined by the setting of the exit needle valve, the gas pressure, and the pressure of the oil in the load piston of the microtensile machine. With this pneumatic-hydraulic appurtenance it was possible to

Jan 1, 1953

By Henry M. Howe

THE natural effect of large size should be to increase segrega¬tion. I have previously pointed' to the excessive segregation in many large ingots as tending to confirm this, but I have shown that in case of ingots less than 16 in. square this expected effect of ingot-size is liable to masked by that of other variables. Under these conditions we should expect that if large ingot-size really does tend to increase segregation, this effect would be shown by taking the average of large numbers of cases, so that the effects of these other variables might off-set and cancel each other.

Jan 10, 1909

By R. T. Webber, R. B. Owen

The vapor phase deposition of molybdenum and tungsten from the hexacar-bonyls has been thoroughly investigated by Lander and Germerl, and shown to yield well-bonded coatings on a variety of hot metallic surfaces. They also demonstrated that chromium coatings2'3 could be similarly deposited, but did not investigate this metal extensively. Recently, conditions have been described by which this compound can be prepared in quantities sufficient for laboratory scale plating experiments, and it is the purpose of the present communication to outline the results of preliminary experiments upon the plating of chromium from its carbonyl. Apparatus and Technique The apparatus used in these experiments is shown in Fig I. At one end, connected by a short length of rubber tubing, is a Cenco Hypervac 20 pumping continuously. At the opposite end is a needle valve which allows a small stream of purified hydrogen to flow through the apparatus. Connected in series are a trap T1, maintained at the temperature of dry ice and acetone, the plating chamber, and two traps T² and T3 containing crystals of the carbonyl. T² is kept in a constant temperature bath (not shown), while T³ is at room temperature. Stopcock S6 allows the hydrogen flow to by-pass the carbonyl traps. A McLeod gauge is connected so that it can measure the pressure at the pump through Se, or the pressure at the plating chamber through S9 and S6. The standard (12 liter) volume connected by Sb is used to determine the volume included by S4, S6, SB, Slot the needle valve and the McLeod gauge. Knowledge of this volume allows calibration of the flow of hydrogen. The apparatus* is built entirely of pyrex, except for the needle valve, the rubber connection to the Hypervac, and the cover of the plating chamber. The plating chamber is water-jacketed, with a large brass top allowing insertion of the specimen to be plated. Set into the brass top is a ground glass stopper through which thermocouple leads are sealed. The thermocouple wires (pure Pt, and 87 pct Pt-13 pct Rh) serve the double purpose of measuring the specimen temperature and suspending it in the chamber. Surrounding the chamber is the coil of an induction heater, H. The apparatus is designed to allow variation of the following conditions: (I) the specimen temperature, from room temperature to about 1000°C, (2) the carbonyl vapor pressure, from 40 to 220 microns, and (3) the hydrogen flow. In several runs, 0.8 to 1.8 PCt of hydrogen sulfide was introuced through a needle valve that replaced S4. The vapor pressure of the carbonyl is

Jan 1, 1949

By V. F. Hollister

The Queen Charlotte gold deposit (also known as the Specogna, Babe, or Cinola) was discovered in late 1970 by Efrem Specogna and Johnny Trico. They were prospecting along the trace of the Sandspit fault, and they sampled jarositic material that included veins from the fault zone. Their assays included some good gold values. They located the Babe Claims in 1971 and optioned them to Kennco Explorations Ltd. Kennco conducted stream sediment and soil geochem studies, geological mapping and drilling of 55.2 m (181 ft) in two drill holes. Kennco withdrew from the property, and by 1977, Cominco, Placer Development, Silver Standard, and Quintana Minerals had each successively worked on the deposit. Consolidated Cinola Mines bought the claims in 1977 and completed exploration of the deposit ultimately in a joint venture arrangement with Energy Reserves. Energy Reserves entered in late 1979, and by 1983, a total of 200 surface and 12 underground drill holes had been completed, totaling 28 600 m (93,832 ft). In addition, a 461.9 m (1515 ft) adit was driven in the ore body. Reserves published by Cinola aggregate 34 Mt (37 million st) of 1.7 g (0.060 oz) Au per tonne. All industry geologists working in the area agree that the Queen Charlotte gold is an epithermal gold deposit in porous volcaniclastic and clastic rocks that is genetically related to a Miocene-Pliocene rhyolite plug. The geologic description here follows the oral presentation made by G. G. Richards, J. S. Christie, and M. R. Wolfhard at a 1976 CIM meeting. Additional comments by the late C. S. Ney of Kennco Explorations are included with the Richards, Christie, and Wolfhard data to complete the geologic set- ting. The attached reprint by Champigny and Sinclair (1 980) provides additional data on the deposit. The Queen Charlotte (Babe, Specogna, or Cinola) gold deposit is located on Graham Island in the northern Charlotte Islands, at the fault boundary of the Skidegate plateau and the Charlotte lowlands. The Sandspit fault marks the physiographic boundary, and it is intruded by rhyolite porphyry at the deposit. Because displaced geochem anomalies, drain- age patterns, and topography suggest dextral and east side down movement for the fault, exposed east block rocks are younger than rocks west of the fault. The east block, which included the ore deposit, is a lowland largely masked by unconsolidated Pleistocene and Recent clastic rocks. Rocks west of the rhyolite plug, on the Skidegate plateau, are Cretaceous carbonaceous and calcareous shale unconformably overlain by a thin veneer of rhyolite tuff. The deposit is about 100 m (328 ft) above sea level. GEOLOGIC SETTING At the ore deposit, the Sandspit fault is a complex structure. However, lithologies on either side of the fault-controlled rhyolite porphyry plug are distinct. West of the rhyolite, the upper member of the Cretaceous Haida formation shale is the most common rock type. The member is composed of dark grey to black, poorly consolidated, and thinly bedded carbonaceous and calcareous shale. The sequence is silicified to an argillite or a hornfels near the rhyolite. West of the rhyolite porphyry plug, but not importantly involved in the mineralization, is a thin masking cover of rhyolite tuff. The tuff unconformably succeeds the cretaceous shale, but it is largely eroded in the mine area. East of the fault-controlled rhyolite porphyry plug is a thick section of conglomerate and sandstone of the Miocene- Pliocene Skonun formation. The ore body occurs within the coarse clastics, the rhyolite intrusive as the western boundary. Ore is entirely contained within the clastics. Original permeability of the clastic rocks was a major control for ore deposition and alteration, and for that reason, the Skonun formation is described in greater detail. The Skonun formation clastics unconformably overlie Haida shale. The Skonun is at least 300 m (984 ft) thick in the mine area, where it trends northerly and dips easterly 15º to 25º. The sequence is about 62 percent conglomerate, 3 1 percent coarse arkosic sandstone, and 7 percent interbedded siltstone and sandstone. Contacts between adjacent beds are generally sharp. Stratigraphic correlations between drill

Jan 1, 1985

By M. M. Leighton

THE engineers of Illinois have been submitting to the State Geological Survey an increasing number of requests for advice on their geological problems, including landslides, unequal settling of fills, laying pavements across peat bogs, shattering and heaving of pavement by frost action, etc. The authors discussed the behavior of landslides, their effects, their causes, a tentative classification, and remedial measures. In the latter connection the efficacy of drainage and how it should be handled in order to be most effective was considered. The principles and efficacy of other remedial measures, such as subsurface blasting, rock anchoring, installation of wood, concrete or steel piling, construction of retaining walls, construction of cribbing and reduction of slope were also discussed. Attention was also given to the matter of applying geological knowledge to avoid undesirable highway locations, and a specific example was cited.

Jan 1, 1929

By Ogden Malin

IN conducting the manufacture of extruded brass rods and brass forgings it has been noticed that there is considerable variation in the physical properties, particularly the machinability of different rods and forgings, even though the composition, working temperatures and method of manufacture remain the same. It is the purpose of this paper to attempt to establish the cause and extent of this variation, and also to determine whether variations in composition within certain defined limits influence hardness and machinability to any marked degree. The writer believes that this variation probably is due to the variation in grain size of the metal, therefore the microstructure of several compositions under various conditions of working were examined in an effort to establish this as a fact.

Jan 1, 1932

E. R. Buckley, Flat River, Mo. (communication to the Secretary*) :—Some statements in the paper of Mr. Keyes relative to the nature and formation of the Ozark lead- and zinc-deposits seen1 to me erroneous and misleading, and I respectfully present the following criticisms, placing Mr. Keyes's original statements in quotations. Referring to the Ozark dome: (p. 192.) "It is a region that has been repeatedly upraised and planed off, until in the middle portion the oldest known rocks only are exposed." Does he mean that the St. Francois mountains, which have always been considered as lying on the eastern flank of the Ozark dome, are the middle of the dome ? Or does he mean that the Cambrian rocks of the generally-accepted middle are the oldest known rocks ? Certainly not the latter, and if the former, his idea of the middle of the dome is not in accord with that of others who are familiar with the region. (p. 203.) "... the ore-deposits are definitely associated with, or localized by, geologic structures of some kind that produce in effect basins in which the underground waters are impounded, or their flow retarded." This statement does not appear to be altogether consistent with the facts, since the ore bodies of the Joplin district, as the rule, occur in those parts of the Mississippian formation which have a tendency to accel erate the flow of ground-water rather than retard it. I migh name the open, brecciated ground near Joplin, Webb City, and Oronogo as especially noteworthy illustrations. The ore-bodies, everywhere, occur in positions where there must have been a free and copious circulation of dilute lead- and zinc-solutions in the presence of reducing constituents. The inequalities in the distribution of the ore-deposits are

Jan 1, 1910

By D. R. Conlon, E. R. Brownscombe

Errors in measurement of reservoir pressure include: (I) gauge errors, and (a) interpretation errors. Gauge errors may be reduced by: (a) reading charts with a comparator microscope, (b) use of hard metal stylus points to give clear lines, (6) insuring temperature equilibrium, and (d) making multiple tests. Check calibrations are equally as important as check well tests. A statistical analysis of such check runs shows quantitatively the advantages of a standardized "zero pressure line'' and of the use of field calibrations made at bottom-hole temperature on the same chart run in the well. Interpretation errors include: (a) fluid heads, which should be corrected to the top of the perforations on the basis of well-fluid gravity and from the top of the perforation to the datum level on the basis of reservoir-fluid gravity, and (b) gradients around the well. Conventional shut-in periods may be entirely inadequate to overcome these, necessitating a reservoir study based on build-up curve data, reservoir history, core analysis and any other available information. Interest in engineering studies of the pressure changes in oil and gas reservoirs is increasing. This type of work yields important information and doubtless will be greatly extended in the future. One of the factors limiting the work, however, is the accuracy with which the reservoir pressures can be determined; for if the inaccuracies in the pressure measurements represent an appreciable percentage of the pressure changes, the engineer is seriously handicapped, and must delay the reservoir study until the reservoir pressure has changed a relatively large amount. This delay can greatly reduce the benefits of such studies, at least from the point of view of aiding the leasing, drilling and completion programs. Thus, from the point of view of reservoir analysis, it is frequently important to obtain the most accurate pressure data possible early in the history of any field—particularly for the gas-distillate fields now being developed. This paper deals with improvements in the measurement of bottom-hole pressures that permit pressures even as high as 4000 or 5000 lb. per sq. in. to be determined with gauge errors of only+ ±I to 2 lb. per sq. in. Since pressures out in the reservoir rather than in the bottom of the hole concern the reservoir analyst, differences between bottom-hole pressures and actual reservoir pressures are also considered. In general, errors in pressure measurement may be divided into: 1. Gauge errors: a. Errors due to inaccuracies in reading the pressure charts. b. Errors due to irreproducibility of the pressure element and recording system. c. Errors caused by failure to allow the gauge to reach temperature equilibrium. 2. Internretation errors: a. Errors caused by a fluid head between the gauge position in tubing and the pressure at the datum level in the reservoir. b. Pressure gradients in the reservoir.

Jan 1, 1946

By D. R. Conlon, E. R. Brownscombe

Errors in measurement of reservoir pressure include: (I) gauge errors, and (a) interpretation errors. Gauge errors may be reduced by: (a) reading charts with a comparator microscope, (b) use of hard metal stylus points to give clear lines, (6) insuring temperature equilibrium, and (d) making multiple tests. Check calibrations are equally as important as check well tests. A statistical analysis of such check runs shows quantitatively the advantages of a standardized "zero pressure line'' and of the use of field calibrations made at bottom-hole temperature on the same chart run in the well. Interpretation errors include: (a) fluid heads, which should be corrected to the top of the perforations on the basis of well-fluid gravity and from the top of the perforation to the datum level on the basis of reservoir-fluid gravity, and (b) gradients around the well. Conventional shut-in periods may be entirely inadequate to overcome these, necessitating a reservoir study based on build-up curve data, reservoir history, core analysis and any other available information. Interest in engineering studies of the pressure changes in oil and gas reservoirs is increasing. This type of work yields important information and doubtless will be greatly extended in the future. One of the factors limiting the work, however, is the accuracy with which the reservoir pressures can be determined; for if the inaccuracies in the pressure measurements represent an appreciable percentage of the pressure changes, the engineer is seriously handicapped, and must delay the reservoir study until the reservoir pressure has changed a relatively large amount. This delay can greatly reduce the benefits of such studies, at least from the point of view of aiding the leasing, drilling and completion programs. Thus, from the point of view of reservoir analysis, it is frequently important to obtain the most accurate pressure data possible early in the history of any field—particularly for the gas-distillate fields now being developed. This paper deals with improvements in the measurement of bottom-hole pressures that permit pressures even as high as 4000 or 5000 lb. per sq. in. to be determined with gauge errors of only+ ±I to 2 lb. per sq. in. Since pressures out in the reservoir rather than in the bottom of the hole concern the reservoir analyst, differences between bottom-hole pressures and actual reservoir pressures are also considered. In general, errors in pressure measurement may be divided into: 1. Gauge errors: a. Errors due to inaccuracies in reading the pressure charts. b. Errors due to irreproducibility of the pressure element and recording system. c. Errors caused by failure to allow the gauge to reach temperature equilibrium. 2. Internretation errors: a. Errors caused by a fluid head between the gauge position in tubing and the pressure at the datum level in the reservoir. b. Pressure gradients in the reservoir.

Jan 1, 1946

By J. E. Andersen, J. Halpern, C. S. Samis

In the presence of oxygen, galena is oxidized in an aqueous medium containing sodium hydroxide, in accordance with the following reaction: PbS + 2O2 + 3OH ? HPbO2 + SO4 = + H2O A novel method was devised for following this reaction which takes place in an autoclave under oxygen pressure, by measuring the concentration of HPbO2- in the solution with a cathode ray polarograph employing stationary platinum electrodes. Using this procedure a study was made of the kinetics of the reaction, in which the effect of a number of variables, including temperature, oxygen pressure, NaOH concentration, and agitation, on the rate, were determined. The results of this study are described and discussed, in terms of possible mechanisms for the reaction. IT is known that sulphide minerals can be oxidized in aqueous media in the presence of oxygen under pressure. Reactions of this type can be classified in two categories depending upon whether the products of oxidation are insoluble or soluble in the aqueous medium. An example of the first type of reaction is the oxidation of pyrite in alkaline solutions, giving rise to an insoluble iron oxide. The kinetics of this reaction have been investigated and its mechanism established.' It has been applied in the oxidation of iron sulphides present in refractory gold ores to improve the subsequent recovery of gold by cyanida-tion.' The second type of reaction finds application where it is desired to recover the metal by leaching during oxidation. In this case a medium is selected in which the oxidized mineral is soluble. For example, nickel, copper, and cobalt sulphide ores can be treated by oxidation in the presence of a solution of ammonia dissolving the nickel, copper, and cobalt as the metal ammine sulphate salts.:' A similar treatment has also been reported to apply to zinc sulphide ores.' It is known that lead sulphate is soluble in solutions of sodium hydroxide or ammonium acetate. It should therefore be possible to dissolve the lead from galena ores by aqueous oxidation with oxygen under pressure using either of these solutions. The applicability of the ammonium acetate treatment has been investigated and confirmed in a recent study.' The present paper describes the results of a similar study in which the kinetics of the oxidation of galena in sodium hydroxide solutions have been investigated. The object of this investigation was pri- marily to obtain information of a fundamental nature relating to the kinetics and mechanism of this reaction. The use of pulps of comminuted ore in a study of this type is undesirable because of the difficulty in controlling and measuring the surface area. The measurements were therefore made using galena crystals of measured surface area and in this way absolute reaction rates were obtained. The reaction was found to proceed as follows: PbS + 2O2 + 3OH ? HPbO2 + SO4 + H2O [I] The products are sodium plumbite and sodium sulphate salts which dissolve in the aqueous solution. The reaction studies were carried out in an autoclave in which a desired pressure of oxygen was maintained. The reaction was followed by measuring the concentration of lead in the solution with a cathode ray polarograph. The results obtained in this investigation are presented and discussed in the present paper. Experimental Materials: The crystals of galena were obtained from Violamac Mines, Sandon, B. C. The following impurities were indicated by spectrographic analysis carried out by the Provincial Assay Office, Victoria, B. C.: Sn, 0.02 to 0.2 pct; Sb, 0.07 to 0.7; Zn, 0.01 to 0.1; Si, Fe, Mg, As, less than 0.05 pct; Ag, 126 oz per ton, the latter determined by standard fire-assaying procedure. After cutting a specimen measuring approximately 5x7x12 mm, the crystal surfaces were ground parallel to the 100 axes using No. 2 emery, washed with water, and the dimensions were measured with a micrometer. Oxygen gas was of commercial grade and supplied in cylinders by Canadian Liquid Air. Solutions were made up with chemicals of chemically pure grade and distilled water. Equipment: Autoclave: The autoclave used in these studies was constructed of stainless steel and

Jan 1, 1954

By W. E. Stiles

A method is presented for predicting the performance of water flooding operations in depleted, or nearly depleted, petroleum reservoirs. The method makes use of permeability variations and the vertical distribution of productive capacity. From these two parameters can be calculated the produced water cut versus the oil recovery. Derivations of the mathematical analogy is shown and sample calculations and curves of prediction are presented. Comparison is made of the predicted and actual performance of a typical 5-spot in an Illinois water flood. INTRODUCTION The use of water as a flooding medium in both depleted and "flush" oil reservoirs is gaining greater recognition and acceptance. Many of the shallower fields, depleted by primary production, have been and are being subjected to water injection in order to obtain some part of the large volume of oil remaining after primary production. Some of the earlier water flood installation proved highly discouraging and the value of water flooding was often questioned. Many of these earlier floods were haphazardly selected and developed as little was known of the physical characteristics and contents of the producing formations. The prior evaluation of the flood performance was impossible. During the past decade the development of the required reservoir engineering tools-—core analysis, reservoir fluid analysis, electric logs, fluid flow formulae, etc.—has allowed the engineer to construct and apply the methods which are presently being used to evaluate the economic and mechanical susceptibility of a reservoir to flooding. This discussion will present a method for taking into account the effect of permeability variations in predicting the performance of water floods in depleted reservoirs. PERMEABILITY AND CAPACITY DISTRIBUTION It is generally agreed by most investigators that in a single phase system fluid will flow in a porous and permeable medium in proportion to the permeability of the medium. Producing formations are usually highly irregular in permeability, both vertically and horizontally. However, zones of higher or lower permeability are often found to exhibit lateral continuity. Thus, while structurally comparable stringers in adjacent wells may differ several fold in permeability values, they usually bear resemblance as being part of a general continuous higher or lower permeability section. It is generally agreed that where such stratification of permeability exists, injected water sweeps first the zones of higher permeability, and it is in these zones that "break-through" first occurs in the producing well. It is a basic assurnption of the presently described method that penetration of a water front follows the individual permeability variations as if such variations were continuous from input to producing well. This is admittedly not rigorously true, but can be justified as making possible a simplifying mathematical approach to an otherwise extremely complicated three dimensional flow problem. As a basis for study of the lateral flow of fluids in formations of irregular permeability, the irregularities may be conveniently represented by a permeability distribution curve and a capacity distribution curve. In obtaining these curves, the permeability values, regardless of their structural position in the formation, are rearranged in order of decreasing permeability. If these permeability values so arranged are plotted against the cumulative thickness, a permeability distribu- tion curve is obtained. This curve may then be likened to a "smoothed" permeability profile of the formation. In making comparison between different distribution curves it is convenient to state the permeabilities in terms of the ratio of the actual permeability values to the average permeability of the formation. These ratios termed "dimensionless permeabilities", are used in this paper rather than the permeabilities in terms of millidarcys. The capacity distribution curve is a lot of the cumulative capacity (starting with the highest permeabilities) versus the cumulative thickness. The capacity and thickness are given as fractions of the total capacity and thickness. Mathematically, the capacity distribution is the intergration of the permeability distribution curve. In practice it is convenient to first obtain the capacity distribution curve and derive from it a smoothed dimen-sionaless permeability curve. The method of obtaining the capacity distribution curve is illustrated in the successive column of Table 1, in which capacity and thickness are derived as fractions of their respective totals. If only a small number of permeability values are available, it is generally desirable to smooth the resultant curve. This has been done to give the capacity distribution curve shown in Figure 1. The differentiation of the capacity distribution curve to obtain the permeability distribution curve is shown in Table 2. Here, the capacity values are read from the smoothed curve at intervals of cumulative thickness, and the increments of capacity are divided by the increments of thickness to obtain the dimensionless permeability, K. Due to this stepwise procedure of calculation these premeability values must be plotted at the midpoints of the successive increments of thickness. The curve so obtained from these data is shown in Figure 1. The total area under the K' curve is equal to unity.

Jan 1, 1949

By W. E. Stiles

A method is presented for predicting the performance of water flooding operations in depleted, or nearly depleted, petroleum reservoirs. The method makes use of permeability variations and the vertical distribution of productive capacity. From these two parameters can be calculated the produced water cut versus the oil recovery. Derivations of the mathematical analogy is shown and sample calculations and curves of prediction are presented. Comparison is made of the predicted and actual performance of a typical 5-spot in an Illinois water flood. INTRODUCTION The use of water as a flooding medium in both depleted and "flush" oil reservoirs is gaining greater recognition and acceptance. Many of the shallower fields, depleted by primary production, have been and are being subjected to water injection in order to obtain some part of the large volume of oil remaining after primary production. Some of the earlier water flood installation proved highly discouraging and the value of water flooding was often questioned. Many of these earlier floods were haphazardly selected and developed as little was known of the physical characteristics and contents of the producing formations. The prior evaluation of the flood performance was impossible. During the past decade the development of the required reservoir engineering tools-—core analysis, reservoir fluid analysis, electric logs, fluid flow formulae, etc.—has allowed the engineer to construct and apply the methods which are presently being used to evaluate the economic and mechanical susceptibility of a reservoir to flooding. This discussion will present a method for taking into account the effect of permeability variations in predicting the performance of water floods in depleted reservoirs. PERMEABILITY AND CAPACITY DISTRIBUTION It is generally agreed by most investigators that in a single phase system fluid will flow in a porous and permeable medium in proportion to the permeability of the medium. Producing formations are usually highly irregular in permeability, both vertically and horizontally. However, zones of higher or lower permeability are often found to exhibit lateral continuity. Thus, while structurally comparable stringers in adjacent wells may differ several fold in permeability values, they usually bear resemblance as being part of a general continuous higher or lower permeability section. It is generally agreed that where such stratification of permeability exists, injected water sweeps first the zones of higher permeability, and it is in these zones that "break-through" first occurs in the producing well. It is a basic assurnption of the presently described method that penetration of a water front follows the individual permeability variations as if such variations were continuous from input to producing well. This is admittedly not rigorously true, but can be justified as making possible a simplifying mathematical approach to an otherwise extremely complicated three dimensional flow problem. As a basis for study of the lateral flow of fluids in formations of irregular permeability, the irregularities may be conveniently represented by a permeability distribution curve and a capacity distribution curve. In obtaining these curves, the permeability values, regardless of their structural position in the formation, are rearranged in order of decreasing permeability. If these permeability values so arranged are plotted against the cumulative thickness, a permeability distribu- tion curve is obtained. This curve may then be likened to a "smoothed" permeability profile of the formation. In making comparison between different distribution curves it is convenient to state the permeabilities in terms of the ratio of the actual permeability values to the average permeability of the formation. These ratios termed "dimensionless permeabilities", are used in this paper rather than the permeabilities in terms of millidarcys. The capacity distribution curve is a lot of the cumulative capacity (starting with the highest permeabilities) versus the cumulative thickness. The capacity and thickness are given as fractions of the total capacity and thickness. Mathematically, the capacity distribution is the intergration of the permeability distribution curve. In practice it is convenient to first obtain the capacity distribution curve and derive from it a smoothed dimen-sionaless permeability curve. The method of obtaining the capacity distribution curve is illustrated in the successive column of Table 1, in which capacity and thickness are derived as fractions of their respective totals. If only a small number of permeability values are available, it is generally desirable to smooth the resultant curve. This has been done to give the capacity distribution curve shown in Figure 1. The differentiation of the capacity distribution curve to obtain the permeability distribution curve is shown in Table 2. Here, the capacity values are read from the smoothed curve at intervals of cumulative thickness, and the increments of capacity are divided by the increments of thickness to obtain the dimensionless permeability, K. Due to this stepwise procedure of calculation these premeability values must be plotted at the midpoints of the successive increments of thickness. The curve so obtained from these data is shown in Figure 1. The total area under the K' curve is equal to unity.

Jan 1, 1949

Jan 1, 1965

By AIME AIME

MODERN metallurgy is an art and a science. The art is process metallurgy-extracting metals from their ores, refining them, and alloying them with one another and with certain nonmetals to produce thereby a variety of metallic materials which, owing to a wide range of useful properties, are for many purposes more valuable to man than the individual metals themselves; process metallurgy also includes shaping or otherwise treating metals and alloys to form objects useful to a complex industrial world. The science is physical metallurgy-organized knowledge of the constitution and internal structure of metals and alloys, of the relation of their composition and structure to properties, and of the laws, theories, and hypotheses that purport to explain this relation.

Jan 1, 1942