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By B. B. Sandiford

It has been known for many years that the efficiency of a water flood can be improved by lowering the water-oil mobility ratio in the system. Such a change leads to better sweep efficiency and also to more efficient oil displacement in the swept zone. Data from our laboratory water-flood tests of both small cores and long sand packs are presented which show that water mobility can be reduced and oil recovery increased by the addition of certain polymer solutions to flood water. The reduction in mobility, in many cases, is greater than would be expected from conventional viscosity measurements. These solutions, however, do not cause significant reductions in oil mobility. The over-all effect of these mobility changes is increased waterflood oil recovery. Encouraged by results of our laboratory work, we expanded our study to include pilot field tests of floods with such solutions. One such test, made in the West Cat Canyon field, Santa Barbara County, Calif., is described in detail in this paper. Three other field tests are also discussed. INTRODUCTION Oil production from most reservoirs following primary depletion and/or water flooding is often less than 50 per cent of the original oil in place. Heavy oil reservoirs seldom yield over 15 per cent of their original oil. With new reservoirs becoming harder to find, the improvement of oil recovery efficiency is one of our very important problems. We describe here some of our attempts to increase the efficiency of oil displacement by adding a water-soluble polymer, partially hydrolyzed polyacrylamide, to flood water. This technique will be termed "polymer solution flooding". The concept of using high-viscosity water to increase the efficiency of water flooding is not new. In 1944 Detling (Shell Development Co.) obtained a patent covering the use of several additives for viscous water flooding.' His objective was to improve water-oil mobility ratios by increasing the viscosity of the flood water. Other patents2-27 have been granted covering specific water-SO~LIble polymers or specific conditions of viscous water flooding. Barnes'" described his laboratory model study of the injection of a viscous water slug into a reservoir which had been partially invaded by bottom water. He concluded that, for this type of reservoir, "the cost of viscous water should not exceed a few cents per barrel for viscous water slug injection to be economically feasible" Our studies have led us to a somewhat different conclusion in a number of cases where hydrolyzed polyacrylamide solutions have been injected into reservoir models or actual reservoirs. Possible reasons for this difference are discussed in this paper. Our studies have shown that polymer solutions may lead to an increase in oil recovery over that from an ordinary water flood by (1) improving sweep efficiency, (2) improving microscopic displacement efficiency, or (3) a combination of these mechanisms. In the work of Barnes, only the benefit of improved sweep efficiency was considered. Also, our work has shown that there are marked differences in the effectiveness of different water-soluble polymers as flood water additives. Partially hydrolyzed polyacrylamide is better than many other water-soluble polymers we have tested because, even in very low concentrations, it can lead to increased oil recovery. This is an important advantage when either a dilute polymer solution is injected continuously or a relatively concentrated slug is injected followed by water. In the latter case! portions of the slug become diluted and function in the formation as very dilute solutions. As dilution takes place the effective slug size will increase which, in turn, will reduce the cost per barrel of the effective flooding medium. The reason that partially hydrolyzed polyacrylamide solutions are more efficient at low concentrations than certain other polymer solutions of equivalent viscosity (when measured in conventional viscometers) is not fully understood. We do know that the shapes and sizes of macro-molecules dissolved or suspended in liquids influence the flow properties of their solutions or suspensions. Solutions of partially hydrolyzed polyacrylamide cause greater reductions in water mobility than would be expected from conventional viscosity measurements. LABORATORY STUDIES Laboratory water floods were run in linear and radial systems with different water-soluble polymers and under varying conditions of flow. including reservoir conditions of temperature, pressure and fluid composition. Some of these runs are considered in this section. OIL DISPLACEMENT IN LINEAR MODELS In this group of runs the sweep efficiency approached 100 per cent because the linear sand packs used were as nearly uniform as possible. Results reflect primarily the micro-scopic displacement efficiencies. The laboratory models were unconsolidat-ed sand packs the lengths of which varied from about 4 in, to 40 ft. Further information on the flow models used is listed in Table 1. Using conventional procedures, water floods were run on sand packs containing either refined or crude oil at restored state. Frequently, a repeat run, similar to the first, was made as a check. Then a third run was made on the restored-state model using either polymer solution or a combination of polymer solution (slug) and water. Details of these runs are also reported in Table 1. In Figs. 1 and 2 results of two different groups of runs are shown in which the oil used was a 62-cp refined oil and the flooding medium

Jan 1, 1965

By S. S. Shen, M. J. Pool, P. J. Spencer

Heats of solution of gold and copper in dilute Au-Cu-Sn alloys have been determined using a liquid metal solution calorimeter. The self-interaction coefficient, Au - has been calculated at constant copper concentrations and n cu has likewise been determined at constant gold contents. Good experimental agreement is obtained between the interaction coefficients and nAu Cc thus demonsbating the reliability of the measured heat values. The measured data are compared with the Predictions of certain solution models. In previous publications,1,2 the results of calori-metric investigations of dilute Ag-Au-Sn and Ag-Cu-Sn alloys have been presented. The present work on the Au-Cu-Sn system concludes a program of studies of enthalpy interaction coefficients in dilute alloys of the Group IB metals with tin. Since the definition and derivation of an enthalpy interaction coefficient has been discussed previously,1,2 no restatement of this theory will be presented here. From the determination of the partial heat of solution of gold and copper in ternary alloys of various copper and gold contents, values of the interaction coefficients can be calculated. These coefficients give an insight into the various solute interactions that occur in the liquid solutions since changes in their magnitude and sign reflect bonding changes that are taking place in alloys of varying solute contents. EXPERIMENTAL Details of the design and operation of the liquid metal solution calorimeter used in this work may be found in a paper by Poo1.3 For the present studies copper of 99.999 pct purity was supplied by American Smelting and Refining Co., gold of 99.999 pct purity by A. D. Mackay, Inc., and tin of 99.99 pct purity by Baker Chemical Co. At the commencement of each series of experimental drops, a tin solvent bath consisting of between 70 and 90 g of the pure metal was inserted in the calorimeter. The weight of the bath was accurately determined and to it were added appropriate amounts of gold or copper to give alloys of the desired composition. For determinations of approximately 0.0015 g-atom samples of Cu were used and for measurements of ?HAu approximately 0.0025 g-atom additions of Au. The heat capacity of the bath was determined at regular intervals during a series of drops using tin calibration samples. Measurements were made of the heat of solution of copper in alloys containing a constant 0.01, 0.02, 0.03, and 0.04 mole fraction of Au, respectively, in order to determine ?HCu in each alloy, and the same mole fractions of copper were used to determine equivalent values for nAu at constant copper concentrations. The composition of the bath was maintained at the desired constant gold or copper content by making calculated additions of the appropriate solute throughout the experiments. The limiting values ?HAu in alloys of constant copper content and of %c, in alloys of constant gold content were studied as a function of the mole fraction of copper or gold respectively in order to determine and nCu. Heat content and heat capacity data used in calculating values of ?ºHAu and ?HCu at the experimental temperature of 720°K were obtained from Hultgren et a1.4 ' RESULTS AND DISCUSSION Determinations of ?HAu. The partial heat of solution of gold in pure tin as a function of gold concentration was determined in the previous study of dilute Ag-Au-Sn alloys1 and can be represented by the least-squares expression: ?HAu(l) =-8075 + 2413xAu [l] which is valid between XAu= 0.00 and xAu = 0.05. The standard error in the constant term, which represents the partial heat of solution of gold at infinite dilution in tin,?HºAu(l)is 35 cal per g-atom, while the standard deviation of the slope, which represents n Au is ± 619 cal per- agtom. Corresponding expressions for ?HAu(l) in alloys containing constant mole fractions of 0.01, 0.02, 0.03, and 0.04 copper were obtained from the data listed in Table I and are themselves given in Table II. Fig. 1 illustrates the partial heat of solution of gold as a function of its concentration in each of the alloys. For the four alloys of constant copper concentration, the values obtained for ?HºAU(l) (in order of increasing copper content) are -8141 i 36 cal per g-atom, -8210 ± 42 cal per g-atom, -8202 ± 46 cal per g-atom and -8268 ± 51 cal per g-atom. The corresponding values of the self-interaction coefficient, n Au, for these alloys are 3103 * 644 cal per g-atom, 2425 ± 676 cal per g-atom, 2574 * 717 cal per g-atom and 2523 ± 899 cal per g-atom. In Fig. 2 these values of n Au are plotted as a function of the copper content of the alloys and are seen to remain approximately constant within the experimental limits. The addition of increasing, small amounts of copper to dilute binary Au-Sn alloys thus has no apparent effect on Au-Au interactions in these dilute liquid solutions, although more exothermic values of ?HºAu(l) do result from an increase in the copper content of the alloys. Analogous behavior was observed with additions of silver to dilute Au-Sn alloys.' By

Jan 1, 1970

By B. S. Blakeney, E. P. Abrahamson II

The effect of the transition elements in binary solid-solution additions upon the recrystallization temperature of iron has been investigated. All these elements immediately raised the temperature, the majority having their greatest effect in less than 0.10 at. pct. A correlation is noted between the rate of change of recrystallization temperature with atomic percent solute and the electron configuration of the solute element. THE work of Abrahamson and rant' on binary chromium-base alloys indicated that a correspondence existed between the effect of each solute element on the brittle-to-ductile transition temperature of chromium and the ground-state electron configuration of the element added. This was felt to be a bonding phenomenon and would be expected to be observed in measurements of other properties involving the breaking or exchange of atomic bonds. From this work it was postulated that a like correspondence should be found for other properties of binary alloys, such as recrystallization. This study is an effort to check this postulation using binary solid-solution iron-base alloys. Previously, the majority of recrystallization studies were carried out on steels. However, Tammann2 investigated the recrystallization of iron as effected by Co, Ni, Si, Mn, Mo, and Cr and stated that elements with the same crystal structure at room temperature as iron appeared to be more effective in raising the recrystallization temperature. Austin, Luini, and Lindsay3 studied the effects of Ni, Cr, Mn, Co, Si, and Mo on cold rolling and annealing, but noted no trend. Abrahamson and rant,' in their work on the effect of both substitutional and interstitial elements upon the brittle-to-ductile transition of chromium, have shown that the outer electron configuration in the ground state of the solute element appears to be the prime determinant of the transition temperature. PROCEDURE All alloys were made using 99.95 + pct Fe with 0.02 wt pct 0, 0.004 pct C, and 0.001 pct N. All alloying elements were 99.9 + percent pure. Metal-lographically the alloys, out to at least 0.1 at. pct, appeared to be in solid solution. Though several published phase diagrams tend to dispute this.4 All alloys were arc melted six times and cast into square 400-g ingots under an argon atmosphere.

Jan 1, 1961

By John G. Reid

Subsequent to extensive laboratory testing, a pilot plant was constructed to further evaluate the process for high temperature copper cementation on iron in continuous operation. The plant was designed to produce 1 to 10 tons of copper a day depending on the copper concentration of the pregnant solution. The energy required to operate the plant was very low as virtually all the solution heating requirements were supplied by the exothermic cementation reaction. The results demonstrated that this, process has potential for commercial application with respect to operating considerations, and yields a copper product in excess of 95% copper at high reaction rates, low iron consumption, and at least 98% copper recovery from solution.

Jan 1, 1976

By John T. Galey

A combination of two factors in addition to the current Federal drilling and price regulations reduced by 120 from I942 the number of new wells completed in southwestern Pennsylvania during the year. No new prospective area was found comparable to the Armbrust gas pool, Westmoreland Co., which accounted for a seventh of the last year's drilling, and it is considered doubtful whether, even if such a field had been discovered, the drilling contractors, who have been seriously affected by the manpower shortage, could have drilled many more wells than they did during the year. New wells totaling 445 were completed for a combined footage of over 1,250,000 Dry holes numbered 131 and had a footage of nearly 400,000. Old wells drilled deeper total 55, of which 17 were found nonproductive. Shallow Development Oil Oil completions yielded an initial of only slightly over one hundred barrels from 21 wells for about the same per well average as that of a year ago. However, 65 bbl. of this total came from two wells in two new strikes. The footage drilled of nearly 33,000 gives an average of nearly I00 ft. less per well than a year ago. Two old wells drilled deeper had a combined initial of only 4 bbl. The largest oil well of the year, 40 bbl., was found in the Speechley (U. Dev.) sand at a depth of 3492 ft. in German township, Fayette County. The location is several miles east of the nearest oil production hut as the area that could be occupied by a pool is fairly well delimited by drilling, the extent of this production would not appear to be large. The other notable oil production was found in the Dunkard (Penna.) sand, Cumberland township, Greene County, at a depth of 1065 ft. Here the first well had an initial of g bbl. and the second 25 bbl. However, a third proved dry, and as this area is also delimited by drilling, the pool doubtless will be of small area. Gas Gas completions yielded an initial of slightly over one hundred million cubic feet per day and new wells, totaling 303, account for all but four million of this volume. Old wells drilled deeper, numbering 35, found gas. The per well average in new drilling of approximately 320 M cu. ft. is nearly 165 M cu. ft. less than a year ago and the total footage is slightly over 830,000, which is about a quarter of a million feet less than in 1942. Average rock pressure of new completions is approximately 365 lb. per sq. in. The entire volume of new production is from the Upper Devonian or higher stratigraphic horizons. In Allegheny County, the grestest activity was in Forward and Plum townships. Wells there account for more than one half the completions. One large well was drilled in Forward township and an open flow of 3.623 million cubic feet was found in an old Gantz (U. Dev.) sand area. The top of the sand was encountered

Jan 1, 1944

By John T. Galey

A combination of two factors in addition to the current Federal drilling and price regulations reduced by 120 from I942 the number of new wells completed in southwestern Pennsylvania during the year. No new prospective area was found comparable to the Armbrust gas pool, Westmoreland Co., which accounted for a seventh of the last year's drilling, and it is considered doubtful whether, even if such a field had been discovered, the drilling contractors, who have been seriously affected by the manpower shortage, could have drilled many more wells than they did during the year. New wells totaling 445 were completed for a combined footage of over 1,250,000 Dry holes numbered 131 and had a footage of nearly 400,000. Old wells drilled deeper total 55, of which 17 were found nonproductive. Shallow Development Oil Oil completions yielded an initial of only slightly over one hundred barrels from 21 wells for about the same per well average as that of a year ago. However, 65 bbl. of this total came from two wells in two new strikes. The footage drilled of nearly 33,000 gives an average of nearly I00 ft. less per well than a year ago. Two old wells drilled deeper had a combined initial of only 4 bbl. The largest oil well of the year, 40 bbl., was found in the Speechley (U. Dev.) sand at a depth of 3492 ft. in German township, Fayette County. The location is several miles east of the nearest oil production hut as the area that could be occupied by a pool is fairly well delimited by drilling, the extent of this production would not appear to be large. The other notable oil production was found in the Dunkard (Penna.) sand, Cumberland township, Greene County, at a depth of 1065 ft. Here the first well had an initial of g bbl. and the second 25 bbl. However, a third proved dry, and as this area is also delimited by drilling, the pool doubtless will be of small area. Gas Gas completions yielded an initial of slightly over one hundred million cubic feet per day and new wells, totaling 303, account for all but four million of this volume. Old wells drilled deeper, numbering 35, found gas. The per well average in new drilling of approximately 320 M cu. ft. is nearly 165 M cu. ft. less than a year ago and the total footage is slightly over 830,000, which is about a quarter of a million feet less than in 1942. Average rock pressure of new completions is approximately 365 lb. per sq. in. The entire volume of new production is from the Upper Devonian or higher stratigraphic horizons. In Allegheny County, the grestest activity was in Forward and Plum townships. Wells there account for more than one half the completions. One large well was drilled in Forward township and an open flow of 3.623 million cubic feet was found in an old Gantz (U. Dev.) sand area. The top of the sand was encountered

Jan 1, 1944

By E. V. Howard

During the recent expansion of precipitate copper production at the Chino Mines Division of Kennecott Copper Corp., Santa Rita, N. Mex., local studies of the dump leaching process were intensified. As these studies progressed, it became apparent that a reliable method for locating leach solutions within the dump was required, since the contact between the leach solutions and the copper-bearing ma.teria1 determines recovery. In the past, the problem of determining leach solution contact has been attacked by various methods, including destructive testing (dump dissection), indirect observation (such as chloride or dye tracers) and mathematical or laboratory model studies, but they have not proved completely satisfactory. The investigation of methods for in situ observation of leach solutions led to consideration of radiation logging in drillholes, which are subsurface techniques used in petroleum exploration and development for locating fluids and measuring porosity. A significant advantage of radiation logging is that, unlike other types of logging, measurements may be made in cased holes, since gamma rays and neutrons will penetrate steel and cement. Three techniques are currently used at Chino: Natural gamma ray logging; neutron-neutron, or moisture logging; and gamma-gamma, or bulk density logging.

Jan 4, 1968

By Frederic Benard

PRIOR to 1936, the Ontario Refining Co. received all incoming blister copper from The International Nickel Company's smelter in the usual form of 460-lb. cakes, or slabs. These were received in open cars in lots of 250 pieces. At the refinery the cakes were unloaded onto narrow-gauge cars, for convenient handling and pickup by charging cranes. In March 1936, an investigation was started on the feasibility of transferring converter copper in the molten state from the smelter to the refinery anode furnaces, a distance of 1 ¼ miles. Although common in steel practice, the transportation of blister copper in this form had not previously been attempted and a preliminary study of the various factors involved was therefore necessary. For this purpose, a series of experiments was made in which molten copper, removed at different stages during the furnace cycle, was held in a small portable holding furnace. This vessel was essentially a refractory-lined steel cylinder provided with ports for filling and emptying, heated by an oil burner. Dimensions of the steel shell were 3 ft. 10 in. diameter by 7 ft. 3 in. long, and thickness of refractories depended on the design and combination used for the particular experiment. The vessel was filled with approximately 2 ½ tons of copper at a predetermined temperature, the lining having been preheated to a definite point by means of an oil burner. All openings were well luted and temperature readings were made every 15 min. by means of an immersion-type thermocouple. In this manner the rate of heat loss resulting with different refractory design could be developed. The ratio of exterior surface to weight of metal was taken into consideration in comparing the experimental results with what might be expected for a full-sized unit, and observations were also made on type and degree of slag accretion. It was not possible to get as much information on this latter point as desirable, but all evidence showed that the problem would be control of slag build-up rather than attack on refractories. From the information derived, and in consultation with the engineering staff of the supplying company, an order was placed for the first

Jan 1, 1938

By E. L. Ickes

DURing the summer and winter of 1918 eleven standard rigs were erected in the United Kingdom to test the petroleum prospects of- ten structures, eight of which were in England and two in Scotland. By the fall of 1921 ten of the wells were completed; the remaining one, the D'Arcy in Scotland, was stopped some months later. The tests were deep ones, five of the wells being 4000 ft. or more, the rest varying in depth between 1810 and 3918 ft. The total footage drilled was 40,047 ft. The holes were put down with standard or cable tools purchased in the United States (except the boilers). The larger sizes of casing, 10-in. and above, were also from America, while the smaller sizes were secured in Scotland. The Hardstoft well in England found a small production of high-grade oil and the D'Arcy well also encountered what is reported as a favorable showing at a depth of 1810 ft. The Werrington and West Calder wells had to be abandoned on account of drilling difficulties. The Apedale well encountered great thicknesses of ash in the Carboniferous and had to be abandoned on account of depth. The results might be summarized by saying that of the ten structures drilled upon, two yielded encouraging showings; three cannot be considered as having been adequately tested; and five produced dry holes, although in some of these small oil showings and gas were met. The total cost of the work amounted to about half a million pounds sterling, which sum includes the cost of all equipment, subsequently sold by the government. The work, under the superintendence of V. L. Conaghan, took place for the most part in the period immediately following the war—a period of high prices, labor and transportation difficulties, and unsettled conditions generally; factors tending to retard the work and affect the costs. The writer, as a member of the staff of S. Pearson & Son, Ltd., had charge of the administration of the work during its later stages and

Jan 1, 1924

By A. E. Back

A method is described in which particulate iron, as distinguished from high purity iron powders used in powder metallurgy, is a precipitant for copper contained in dilute solutions. A new precipitation apparatus utilizes particulate iron precipitants to recover copper more efficiently than is possible in a conventional launder precipitation plant. In the search for lower cost methods of recovering copper from mine water, the use of sponge iron or particulate iron (as distinguished from iron powder used in powder metallurgy) as precipitants in place of tin cans, detinned scrap iron, or scrap iron is an intriguing possibility. The relatively faster copper precipitation rate obtained with particulate iron as compared to scrap iron promises economic and processing advantages when, and if, particulate iron becomes competitive cost-wise with available scrap iron. Kennecott has developed a precipitation cone,' see Fig. 1, utilizing various particulate iron precipitants and has demonstrated the process successfully in a prototype at a flow rate of approximately 1000 gal of solution per min. Essentially complete precipitation of copper is obtained, the cone overflow solution is clear and contains no particulate copper, and the iron factor is more favorable than in a conventional launder plant. Initially, sponge iron produced at the Ray Mines Div. Kennecott Copper Corp. for use in a Leach-Precipitation-Flotation process was used in exploratory tests to develop a suitable apparatus to take advantage of the rapid precipitation rate and efficient iron utilization for the recovery of copper from dilute solutions. Here it was demonstrated that, when sponge iron was added to a launder, the particles of iron collected in the bottom of the launder and tended to cement together. This resulted in incomplete precipitation of the copper and inefficient utilization of the iron. Next, sponge iron was suspended in glass columns to study the dynamics of the precipitation reaction. Again it was observed that the particles tended to cement together at low solution flow rates, while at higher flow rates large amounts of the precipitant overflowed the column, resulting in loss of precipitant and an inefficient process. Next, the precipitant was suspended in an inverted cone in a rising column of solution. Dynamic suspension of the solids was maintained at relatively rapid solution flow rates with instantaneous and complete precipitation of copper and with improved iron utilization. The first tests were conducted on a batch basis and it was determined that a dynamically suspended bed of precipitant was necessary for satisfactory operation. More than 99% of the metallic iron could be converted to metallic copper by careful control of the residence time in the cone and copper precipitation was essentially complete, even when the available iron precipitant was almost depleted. Several cones were built, ranging in capacity from 1 to 200 gal of feed solution per min, and finally, a prototype cone was constructed which was 20-ft high

Jan 1, 1968

By G. Rowan, M. W. Clegg

Approximate analytical solutions for non-Darcy radial gas flow are derived for bounded and infinite reservoirs producing at either constant rate or constant pressure. These analytical solutions are compared with published results for non-Darcy flow obtained on digital and analogue computers, and the agreement is show to be very good. Some observations on the interpretation of gas well tests are made. INTRODUCTION The flow of gases in porous media is a problem that has been the subject of much study in recent years [l - 71 , and many methods have been proposed for solving the non-linear equations associated with it. The assumption that the flow satisfies Darcy's Law It has been observed, however, that the linear relationship between the flow rate and pressure gradient is only approximately valid even at low flow rates, and that as the flow rate increases the deviations from linearity also increase. It has been suggested by a number of authors that Darcy's Law should be replaced by a quadratic flow law of the form This form of equation was first suggested by Forchheimer [9] and, later, Katz and Cornell [10], and Irmay [lll, developed a similar equation. Houpeurt [12] derived this form of equation using the concept of an idealised pore system in which each channel consists of sequences of truncated cones giving rise to successive restrictive orifices along the channel. This type of representation leads to a quadratic flow law of type [4], for all fluids, but it is found that the quadratic term is only significant in the case of gas flow. The methods of Houpeurt for solving gas flow problems will be discussed further in another section of this paper. Solutions of the non-linear equation for Darcy gas flow 121 may be classified as either computer (digital and analogue), or approximate analytical ones. The former include the well-known solutions of Bruce et al. [13], and Aronofsky and Jenkins [14] , but the latter solutions, apart from the simple linearisation of equation (2) to yield a diffusion equation in p2 , are not so well-known. Amongst these approximate analytical solutions should be mentioned the work of Barenblatt [IS], who has applied the techniques of dimensional analysis to obtain similarity solution to a large class of non-linear equations; also, a number of Russian authors, including Barenblatt [16] , Kim [17] and others, who have used the method of moments for obtain-

Jan 1, 1965

By S. D. Dahlgren

ORDERED G.P. zones having the cesium chloride structure were found to exist in the bcc iron-rich grains of an Fe-Au-Cu alloy that had been supersaturated with approximately equal atomic percentages of gold and copper, and aged at 400° and 350°C. Streaks and superlattice spots in electron diffraction patterns revealed the presence of the ordered zones in the aged material. The ordered Ll2 structure is commonly found for precipitates in fcc metals (e.g., Ni3A1 in nickelL7') but it is uncommon to find precipitates in bcc metals having the cesium chloride structure. The formation of the G.P. zones caused age hardening of the grains. Samples containing 3.8 at. pct each of gold and copper (with the remainder being iron) were annealed at 95@ or 1125°C in quartz capsules and were quenched by breaking the capsules under water. X-ray diffraction patterns revealed two solid solutions in the quenched samples. One solid solution was bcc and the other was fcc. The microstructure consisted of iron-rich grains of 0.3 mm diam surrounded by a yellow gold-copper-rich grain boundary network. The Au-Cu phase diagram %hows continuous solid solubility of gold and copper with ordered phases forming below 410°C. None of the ordered Au-Cu phases have the cesium chloride structure. Both Fe-Au and Fe-Cu phase diagrams3 show extended miscibility gaps and only terminal solid-solution phases. Consequently, it is reasonably certain the iron-rich grains consisted of an a-phase terminal solid solution, and the grain boundary network consisted of a gold-copper-rich terminal solid solution. Lattice parameters of the quenched solid solutions were consistent with the suggestion that the quenched phases were terminal solutions. The lattice parameter of the bcc phase (2.879A) obtained upon quenching from 950°C was higher than that (2.866A) for pure iron. The fcc phase in this sample had a lower lattice parameter than that for a 50 at. pct Au and 50 at. pci Cu solid solution, i.e., 3.866 compared to 3.877A. The lattice parameter for the 50 pct Au and 50 pct Cu solid solution was interpolated from data for Cu-Au solid solutions.4 More gold and copper were soluble in iron at 1125°C than at 950°C as indicated by a 0.012A increase in the bcc lattice parameter for a sample quenched from 1125°C. After the alloy had been quenched from 950° and 1125°C, the bcc lattice parameters were 2.879 and 2.891A1 respectively G.P. zones having the cesium chloride structure-which formed during low-temperature aging—were detected by electron diffraction and observed with electron transmission microscopy. In Fig. 1, the asymmetrical streaks parallel to ( 100) directions indicate that platelike G.P. zones had formed parallel to (100) planes of the matrix. The direction of streak asymmetry shows that the bcc unit cell of the G.P. zones was larger than the bcc cell of the matrix. The ordered cesium chloride structure is indicated by low-intensity superlattice spots at 010 positions which are nonallowed for bcc structures. The superlattice spots are streaked; therefore they are from the G.P. zones and are not caused by rel-rod effects of a thin matrix phase. The appearance and size of the zones observed in electron transmission microscopy and the appearance of the asymmetrical streaks in the electron diffraction patterns for the Fe-Au-Cu alloy were the same as those observed for a similarly treated Fe-Au alloy.' Ordered G.P. zones were detected also for an Fe-Au-Cu sample aged only at 400°C. The production of the ordered cesium chloride structure zones by low-temperature aging of super-

Jan 1, 1968

By W. W. Simpson, W. L. Staker, R. G. Sandberg

The Bureau of Mines investigated selective extraction of Au and Ag from a low-grade Au ore containing Hg. Gold and silver were extracted from the ore in cyanide slurries, and Hg extraction was suppressed with sodium or calcium sulfide. Maximum Au extraction and minimum Hg extraction were obtained using solutions containing 17 kg NaCN/t of solution (0.34 lb NaCN/st). Increasing the cyanide concentration increased Hg extraction without increasing Au extraction. Mercury extraction from the ore was suppressed with 0.5-2.9 kg CaS/kg Hg (0.5-2.9 lb/lb) in the ore. Gold-to-mercury ratios of 100:1 to 400:1 were obtained in the leach solution, and on the activated carbon in a CIP circuit.

Jan 1, 1985

By G. Wranglen

On account of the possibility of isolating carbides in steel it is generally assumed that the electrode potential of iron carbide is more noble than that of ferrite.1,2,3,4,5 Differences from 0.032 V1 to 0.4 V4 have been recorded. However, it is important to realize that the more noble behavior of cementite in relation to ferrite is not an issue of thermodynamics but of reaction kinetics. Theoretically, cementite is less noble than ferrite, which is a direct consequence of its thermo-dynamic instability. With the value ?F°298 = +4700 cal per mol for the free energy of formation of cementite6 it is easily calculated that the electrode

Jan 1, 1950

By W. G. Cornwell, R. J. Hisshion

The development of a process for the treatment of telluride concentrates at Emperor Gold Mining Co. Vatukoula, is discussed. The concentrate is produced by flotation in cyanide solution immediately after milling. Two stages of cleaning are employed and a high-grade concentrate is produced usually containing more than 50% of the precious metal. The process developed in the first instance involved batch roasting followed by batch leaching in strong cyanide solution, recovering gold and silver only. The procedure currently employed is chemical oxidation of the tellurides using hypochlorite as the oxidant in a basic solution of a caustic soda and sodium carbonate. After oxidation the gold and silver are recovered by cyanidation. The residue is then leached with sodium sulfide and elemental tellurium precipitated with sodium sulfite.

Jan 1, 1977

By Thomas E. Bruner

With drilling costs playing a pivotal role in the economics of most mineral exploration programs, there has been a significant effort over the past decade to trim expenditures in this area. One result of these cost-cutting measures has been the substantial shift to use of rotary drills. By the mid-1970's, rotary drilling accounted for six times as much footage as core drilling in exploration work. Among the various rotary drilling techniques, the use of dual-tube drilling for continuous sampling is attracting growing interest. Factors such as drilling speed and cost advantages, coupled with favorable comparisons between chip samples and solid core samples, have helped to spark this interest.

Jan 4, 1979

By D. de Fontaine

A convolution procedure is described for obtaining an analytical expression for the composition profiles of solute concentration:; in binary solid solutions. The free energy of solutions containing such compositional inhomogeneities can then be evaluated and the stability of spherically symmetric clusters (G.P. zones, for short) us a function of their radii and central compositions can be studied accordingly. Two characteristic zone radii are defined: the minimum radius (RM) corresponding to the smallest zone for which growth is energetically favored over dissolution, and the critical radius RK) corresponding to zones associated with the minimum work of formation. The values of RM and RK coincide at the two classical limits of nucleation and growth and spinodal decomposition. As the spinodal is approached, however, RM and RK diverge increasingly and it is proposed that the initial] decomposition morphology is governed more closely by the minimum, rather than by the critical radius since the former possesses no singularity within the m eta stable phase boundary. Reversion is briefly discussed in the light of the foregoing and it is shown that a set of reversion temperatures located between the coherent miscibility gap and the coherent spinodal must correspond to a given distribution of low temperature zones. SINCE the early works of Guinier1 and preston,2 the kinetics and morphology of GP zones have been studied extensively, see Ref. 3, for example, for a recent review. Nevertheless, a completely satisfying theoretical treatment of the decomposition of meta-stable or unstable binary solid solutions is still lacking due to the almost unsurmountable mathematical difficulties that one encounters in attempting to solve the pertinent diffusion equation which, in principle, describes the whole process. This equation, first derived by Cahn for the initial stages of spinodal decomposition,4 is a nonlinear partial differential equation of the fourth order in anisotropic space, a general analytical solution of which is completely out of the question. From this equation, some prediction can be made, however, concerning the later stages of spinodal decomposition5 and a recent numerical solution6 of the equation in the case of one- and two-dimensional composition modulations of a solid solution inside the spinodal has led to the following considerations: the sinusoidal morphology7 is to be expected only for solutions of average composition c, located near the center of the coherent miscibility gap.8 For solutions with co closer to the spinodal decomposition, depleted shell zones9 should constitute the first recognizable decomposition product, later evolving to iso- lated, enriched preprecipitates in a uniformly depleted matrix as this must, in all cases, constitute the final metastable morphology, barring, of course, loss of coherency and change in crystal structure. In agreement with the qualitative description of Bonfiglioli and Guinier,l0 it thus appears that the various models discussed by previous authors are, in fact, idealized successive stages of the general decomposition process. Unfortunately, corresponding calculations for a solid solution outside the spinodal are not yet available because of two additional difficulties: it is essential that the diffusion equation be solved in three-dimensional space, and furthermore, one must include in the equation an appropriate "source term" describing the statistics of the creation of composition fluctuations required to trigger the nucleation events. At present, a general treatment of this problem does not appear to be tractable. Nevertheless, by using a modelistic approach, i.e., by selecting a priori certain composition variation profiles and by evaluating their associated free energies, one can draw certain conclusions relative to the stability of these isolated composition modulations or "zones", both outside and inside the spinodal. This is the object of the present investigation. THEORY We shall now describe a standard four-parameter spherically symmetric GP zone, evaluate its free energy according to the Cahn and Hilliard11 formula (Eq. [5], below), and plot the corresponding energy surfaces as a function of zone amplitude and radius as

Jan 1, 1970

By Pradeep K. Rohatgi, Clyde M. Adams

Structures obtained on freezing of several hypo-and hypereutectic Al-Cu alloys over a range of solidification rates have been examined. Dendrite spacing, L, increases linearly with solute concentration and with the square root of the inverse freezing rate. The relationship for hypoeutectic alloys is: where rate of change of fraction solid with time, is freezing rate, C is solute concentration, (pct Cu)=1. Mass transport in inter dendritic liquid during solidification is analyzed; the experimental observations suggest maximum concentration differences and constitutional supercooling in the inter dendritic liquid increase with an increase in the solute concentration. The dendrite morphology changes with freezing rate and alloy composition. The dendrites of the a phase are parallel, uniformly spaced plates with slow freezing and rods with rapid freezing. Nonor-thogonal side branching has been observed in phases with cubic and tetragonal structures. Side branches in a dendrites are orthogonal with slow freezing and at 60 deg with rapid freezing. Formation of second-phase envelopes around the Primary phase is also discussed. DENDRITIC structure is characteristic of many types of phase transformation. The most extensively studied so far has been solidification of liquid solutions. chalmersl and coworkers have interpreted the formation of dendrites in terms of the breakdown of a planar interface. Most of the work done concerns itself with the development of an instability at the interface. Little theoretical work has been done quantitatively to relate the parameters of dendritic structure to mass transport in the liquid phase. A few empirical relations based on the experimental2'3 observations exist in the literature. Several workers2 including Brown and Adams1 have studied dendrite spacing in A1-Cu system as a function of solidification variables. In most cases, dendrite spacing has been found to increase linearly with the square root of some parameter proportional to the freezing time. The effect of solute concentration is not clear; some workers report the dendrite spacing increases with solute concentration4 whereas others report vice versa.''' ~ohatgi' has observed an increase in the spacing between ice dendrites with an increase in solute concentration in water. Tiller has also suggested that dendrite spacing should increase with solute concentration. In the present work dendrite spacing and morphology have been examined as a function of solute concentration and freezing rate. The freezing rate is defined as the fraction of liquid solidified per unit time, dfs/dß?, where f, is the fraction solid and 8 the time. The fastest freezing rate studied was 4550 times the slowest freezing rate. THEORETICAL CONSIDERATIONS It is of interest to analyze the concentration distribution in the liquid phase between growing dendrites during solidification, Fig. 1. Since this distribution is a direct consequence of the rejection of solute by the growing solid, a diffusional process, the concentration gradients increase with the freezing rate. However, when solidification rate is the only variable in a series of experiments, the interdendritic liquid regions become smaller (i.e., the dendrites become more closely spaced) with an increase in freezing rate. The main purpose of the analytical treatment of interdendritic liquid diffusion will be to reveal a tendency for dendrite spacing to decrease with increasing solidification rate in just such a way that the maximum concentration differences developed in the liquid phase are remarkably independent of freezing rate. Two rather different analyses are set forth, one pertaining to the one-dimensional diffusion which obtains in the interdendritic liquid between parallel plate-shaped dendrites, and the other to the cylindrically symmetrical diffusion around rod-shaped dendrites during early stages of solidification. The results of the two analyses are quantitatively similar, correlating dendrite spacing, maximum concentration difference, and freezing rate. First consider the simpler one-dimensional case. Two parallel plate-shaped dendrites are separated by a distance, L, between centers, Fig. 1. Solidification takes place by the thickening of these plates, with solute being rejected into the liquid. It is assumed there is no diffusion in the solid. This thickening process is slow enough and the dendrite spacing small enough that the concentration differences which develop, although interesting and important, are very small (an important assumption which is verified ex-

Jan 1, 1968

By M. E. Lombardi

THE cost of maintaining the production of an operating oil company is one of the most important, as well as one of the most difficult to estimate, of the various items which go to make up the total cost of producing oil. In the opinion of many operators the cost of drilling and developing new wells, whose production takes the place of the loss in production through decreased yield of the old wells, is considered an operating expense, for the reason that the total income-producing power of the property is not increased. The cost of these new wells may be added directly to production expense, or it may he charged to capital account, and this account depreciated to the same extent. In either case, after an oil company is on a satisfactory income-producing basis, the money for drilling new wells to maintain production must be taken from the income of the company. Three factors determine the cost of maintaining production: First, the rate of decline in yield of the wells; second, the cost of drilling and equipping new wells in terms of their production; third, the decrease in initial production of new wells as the property is drilled and gas pressure taken off the sands, etc. In order to check theoretical figures for the cost of maintaining production the writer, with the assistance of Reed Bush and Fred Tough, has compiled the following figures. It is necessary first of all to choose a period of time during which production for the field or territory studied remains fairly constant. The longer the period of time over which this condition prevails, the better. It is also necessary to eliminate or allow for any extraneous condition which may have affected the production returns, such as the shutting clown of a large number of wells, the bringing in of a well of exceptionally large yield, the opening up of virgin territory where the flush yield is greater than will he had from new wells in after years, etc.

Jan 9, 1915

By Allan Martin, R. A. Swalin

Diffusion rates of manganese, aluminum, titanium, and tungsten in nickel were measured at temperatures between 1100° and 1300°C. Activation energies, Q, and values of the frequency factor, Do, were calculated for each system. Values of Q were found to be within 15 pet of that for self-diffusion of nickel in agreement with present theories of diffusion. ONE of the most interesting problems in diffusion concerns factors governing the order of diffusion coefficients of various solutes in a common solvent metal at low solute concentrations. An early suggestion by Rhines and Mehl' was that diffusion coefficients might each approach that of the self-diffusion coefficient of the solvent itself. Later Thomas and Birchenall' pointed out correlations between the order of the diffusion coefficients and the freezing point depressions of the solvent by the various solutes. Other correlations have been sought. To settle this question it seems likely that much more data will be needed and, in particular, data collected at low solute concentrations. This type can be obtained by special analytical techniques as well as by use of radioactive tracers. The following study was made of diffusion of manganese, aluminum, titanium, and tungsten in a common solvent, nickel, at relatively low solute concentrations: 1—Production of alloys of nickel with manganese, aluminum, titanium. and tungsten at concentrations of the order of 1 atomic pet. 2—Use of pressure-welded diffusion couples in cylindrical form. 3—Diffusion anneals in the temperature range of 1100" to 1300°C. 4—Lathe sectioning of the diffused couples. 5—Spectrophotometric analyses of lathe turnings for the solute being studied. 6—Calculation of the diffusion coefficient for each of the solutes as a function of temperature. 7—Interpretation of results with current theories of diffusion. Experimental Work Materials—Two types of nickel were used in this research. The grade designated as Vacuum melted Mond nickel was used for all diffusion systems except the Mn-Ni system for which the Vacuum melted electrolytic nickel was used. Analyses of the two grades are given in Table I. The manganese used in making alloys was 99.9 + pet pure, aluminum 99.99 pet pure, titanium 99.9 pet pure, and tungsten of C.P. grade powder. Alloys used in this investigation were prepared by melting in vacuo or under a low pressure of argon. After melting, all heats except those of nickel-manganese were poured into a cylindrical copper mold 3 in. long and 1 in. ID. In the case of nickel-manganese, the alloys were solidified in the melting crucible. For nickel-aluminum heats alumina crucibles were used and for all other heats, zirconia crucibles.

Jan 1, 1957