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By E. O. Karenna, A. D. Smigelskas

This is the third paper in a series on the diffusion of zinc in alpha brass.' At the time of the first paper it was accepted that diffusion in a substitutional type of solid solution depended upon an equal interchange of solute and solvent atoms across the diffusion interface (or past a given lattice reference point). Discrepancies in the size of the areas under the diffusion curves on each side of the interface, if observed, were explained on some other basis than the fact that the solute atoms might cross the diffusion interface without an equal number of solvent atoms diffusing across the interface in the opposite direction. The second paper presented evidence indicating that zinc atoms in alpha brass diffuse across the interface more rapidly in one direction than the copper atoms diffuse across the interface in the opposite direction. This phenomenon forced the interface to move in the opposite direction of the diffusion of zinc atoms to provide space for the additional zinc atoms dissolved in the alpha brass. That the interface and columnar grain structure on one side would remain intact during this mass movement was not expected; how ever, it is gratifying that they did. While the evidence was sufficiently satisfying to the author, it was decided that additional experiments were in order to prove that zinc diffuses more rapidly than copper in alpha brass. It is the purpose of this paper to present the results of these experiments. Procedure A bar of 70-30 wrought brass was selected, to avoid the relatively large volume change in going from beta to alpha brass as in the previous investigation. A bar 7 in. (18-cm.)* long and about 3/4 in. (1.9 cm.) wide was surface ground and polished with abrasive paper on plate glass to 0.4184 0.0002 in. (1.062j + 0.0005 cm.) thick. Six0.00j-in. (0.013-cm.) diameter molybdenum wires, chosen because of their very low solubility in coppcr and alpha brass, were strctched lengthwise along each of the two plane surfaces. Glass tubes placed at right angles to the wires every 1/2 in. held the wires tightly against the brass. The sample was then emersed in an acid copper sulphate plating bath and electroplated to a depth of about 0.020 in. (0.050 cm.) copper on all sides. The glass tubes were no longer necessary to hold the molybdenum wires in place and were removed. The sample was then electroplated to a depth of

Jan 1, 1947

By R. S. Dean. J. R. Long, T. R. Graham

Although considerable information has been published concerning manganese additions to the aluminum bronzes, these data refer principally to the two-phase alloys containing 8 to II pet aluminum, with some incidental information on the single-phase alpha solid solution alloys. Straussl gives an excellent review of the literature on aluminum bronzes up to 1927 and a bulletin2 of the Copper Development Association brings the bibliography up to 1938. The most extensive work on manganese addition is that of Rosenhain and Lantsberry,3 who investigated alloys ranging up to 10 pct aluminum and up to 10 pct manganese, and presented data on the physical properties of sand-cast, chill-cast, and several wrought alloys. The greater portion of the work, however, concerns alloys ranging from 7 to 10 pct aluminum in the cast condition and sheds little light on the properties of wrought single-phase alloys. Corson4 notes that alloys containing 10 pct manganese and 4 pct aluminum are not hardenable by heat-treatment, while one with 15 pct manganese and 5 pct aluminum can be hardened, but he gives no tensile data on it. In fact, no systematic study of the properties of single-phase wrought alloys containing substantial amounts of manganese has been reported. It should also be noted that most of the investigators worked with alloys containing significant amounts of iron and silicon, and that these impurities, whether intentionally added or accrued from the raw materials used in the preparation of the alloys, may be expected to have a direct bearing on the resultant properties. In the work on alloys made with electrolytic manganese, the Bureau of Mines has undertaken an investigation of the copper-manganese-aluminum system for the purpose of establishing the constitution and properties of high-purity alloys. In a recent paper6 the authors reported a metallographic investigation of the alpha solid solution area and the adjoining fields of the copper-manganese-aluminum system up to 50 pct manganese. This study established the alpha-phase boundaries at 50" temperature levels from 400' to 850°C. It was found that the addition of manganese to copper-aluminum alloys decreases the solub%ty of aluminum in the alpha phase (Fig I), curving the boundary toward the copper-manganese base line. The greatest change occurs in the first 20 to 25 pct manganese, which decreases the solubility of aluminum to approximately 4 pct. With larger amounts of manganese the alpha boundary tends to parallel the copper-manganese binary. At 13oo'F and higher,

Jan 1, 1947

By C. L. Burrill

The forecasts presented in this paper constitute an attempt by the writer to predict the pattern of the consumption of petroleum products in the United States during the period of transition from war to peace. Although, in preparing the estimates, secular trends were not overlooked, greater emphasis was placed upon considerations of a cyclical character, or upon influences which might be peculiar to parts of the period. The estimates do not extend beyond the year 1950 because by then conditions in the industry should have returned to normal. The consumption of petroleum products is affected, of course, by changes in the condition of business in general. Before estimates of petroleum consumption could be prepared, therefore, it was necessary to predict the pattern of general business during the period under review, particularly the economic series that in the past have shown the closest relationships with petroleum consumption. It is the writer's view that business activity in this country (as measured by industrial production) will be higher on the average during the period between the end of the war and the year 1950 than it ever was before during a peacetime period of the same duration. When the war is over, consumers will have saved amounts of money that will be very large as compared with any previous accumulations. There is little question, therefore, as to the financial ability of consumers to purchase goods. The production of many durable consumers' goods, such as automobiles, refrigerators and radios, has been completely stopped since early in the war; also, many semidurable and nondurable consumers' goods have not been available in the quantities or the qualities desired. There is considerable needi therefore, for consumers to purchase goods after the war. The important question is whether consumers will purchase goods in "1arge enough quantities to keep our economy running at a high level. The writer answers this question in the affirmative. The mere existence of very large consumer savings lends considerable support to this view because, with such backlogs of " security," consumers can afford to spend more of their current earnings than they otherwise could. Also, several polls have been taken, which indicate that consumers expect to buy large quantities of a variety of goods. Some of the savings, therefore, probably will go into current consumption. Even though this percentage is relatively small, so that the bulk of the funds accumulated by consumers during the war continues to remain as savings during the period under review, spending should be great enough to start the production cycle and keep it

Jan 1, 1945

By J. R. Long, T. R. Graham, R. S. Dean

ALTHOUGH considerable information has been published concerning manganese additions to the aluminum bronzes, these data refer principally to the two-phase alloys containing 8 to 11 pct aluminum, with some incidental information on the single-phase alpha solid solution alloys. Strauss1 gives an excellent review of the literature on aluminum bronzes up to 1927 and a bulletin2 of the Copper Development Association brings the bibliography up to 1938. The most extensive work on manganese addition is that of Rosenhain and Lantsberry,3 who investigated alloys ranging up to 10 pct aluminum and up to 10 pct manganese, and presented data on the physical properties of sand-cast, chill-cast, and several wrought alloys. The greater portion of the work, however, concerns alloys ranging from 7 to 10 pct aluminum in the cast condition and sheds little light on the properties of wrought single-phase alloys. Corson4 notes that alloys containing 10 pct manganese and 4 pct aluminum are not hardenable by heat-treatment, while one with 15 pct manganese and 5 pct aluminum can be hardened, but he gives no tensile data on it. In fact, no systematic study of the properties of single-phase wrought alloys containing substantial amounts of manganese has been reported. It should also be noted that most of the investigators worked with alloys containing significant amounts of iron and silicon, and that these impurities, whether intentionally added or accrued from the raw materials used in the preparation of the alloys, may be expected to have a direct bearing on the resultant properties. In the work on alloys made with electrolytic manganese, the Bureau of Mines has undertaken an investigation of the copper-manganese-aluminum system for the purpose of establishing the constitution and properties of high-purity alloys. In a recent paper5 the authors reported a metallographic investigation of the alpha solid solution area and the adjoining fields of the copper-manganese-aluminum system up to 50 pct manganese. This study established the alpha-phase boundaries at 50° temperature levels from 400° to 850°C. It was found that the addition of manganese to copper-aluminum alloys decreases the solubility of aluminum in the alpha phase (Fig I), curving the boundary toward the copper-manganese base line. The greatest change occurs in the first 20 to 25 pct manganese, which decreases the solubility of aluminum to approximately 4 pct. With larger amounts of manganese the alpha boundary tends to parallel the copper-manganese binary. At 1300°F and higher,

Jan 1, 1947

By R. M. Waterstrat

The phase VPt has been reported to have a crystal structure of the B19 (AuCd) type at low temperatures.''' A recent investigation3 has indicated that this phase forms by an ordering reaction from the disordered fcc Pt(V) solid solution which is stable at high temperatures. olander4 has shown that there exists a close structural relationship between the orthorhombic B19 structure and a fcc structure possessing the L1 , (CuAu) type of atomic ordering. One may derive the B19 structure by a shear-like displacement of the atoms in the (002) plane of the ordered fcc lattice along the (010) direction through a distance equal to one eighth of the unit cell dimension, see Fig. 1, followed by an orthorhombic distor; tion of the cube axes such that a = 2.693A. h = 4.413A. and c =4.767A (estimated uncertainty 0.005A). Filings of this phase were produced by grinding a VPt alloy having the B19 structure with a diamond dental grinding disc. When these filings were subjected to X-ray diffraction examination, a pattern of a severely cold-worked fcc structure was obtained. higher solution temperature used (1200 C) or to a much lower oxygen pressure than he reported, due to transfer through many bends and tubes in his complicated apparatus. An interesting observation was made when an oxygen addition was attempted in a cylindrical sample of columbium in the cold worked condition rather than in the annealed condition. The interior of the sample re-crystallized during the oxygen addition at 900°C. The periphery, however. (1 mm) did not recrystallize. A similar sample without oxygen recrystallized throughout the entire cross section. It appears that the re-crystallization is hindered by interstitial oxygen. Presumably, the interior recrystallized before appreciable oxygen could diffuse into the core. This work was supported by the United States Atomic Energy Commission. When the filings were annealed in a high vacuum furnace for 15 min at 110O0C, however. they returned to the B19 structure perhaps as a result of reordering. Subsequent less-severe cold-working of these filings by grinding in a hardened steel mortar and pestle at room temperature produced a transformation into a cold-worked L1, structure which was slightly tetragonal. Thus it appears that the degree of deformation may influence the final structure. Considerable line-broadening was observed in X-ray diffraction patterns obtained from the cold-worked filings and therefore no attempt was made to obtain accurate lattice parameters. Vacuum annealing treatments at 1100'C intended

Jan 1, 1970

By Carl F. Floe, Michael B. Bever

THE possibility that carbon may be soluble in copper to a limited extent has been recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are frequently used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. REVIEW OF LITERATURE In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of o.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.92 58 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy's request, Dick,3 in 1856, carried out various working tests on copper that had been in prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as o.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick's experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1945

By Irving M. Symonds

Compania Minera de Penoles, S. A., at its Avalos unit operates a lead-zinc concentrator having a capacity of about 600 short tons per day. Lead and zinc concentrates are made by flotation methods. The concentrator is at Terminal de Provi-dencia, in the state of Zacatecas, some 70 miles south of Saltillo, Coahuila. The Penoles-Avalos railroad operating between the plant and Estacion Avalos, a distance of 6 miles, makes connections with the Coahuila and Zacatecas railroad, which in turn connects with the Nacionales de Mexico at Saltillo. The three railroads are each of different gauge, requiring the transfer of all supplies and concentrates at each junction. The mill operates on company ores, on ores from leased mines, and as a custom mill. The custom business is very small. The lead concentrates are shipped to company smelters at Monterrey, Nuevo Leon and Torreon, Coahuila. Since the European war, all zinc concentrates have been shipped to the United States. Ore Treated The major source of ore supply is a group of four mines owned or leased by the company, some three miles south of the mill in the mountains, from which the ore is delivered to the mill by a gravity aerial tramway. Custom ore comes in by rail. The ores occur in chimneys. The upper levels contained oxidized siliceous ores of lead, copper, silver and gold, with varying amounts of zinc. These ores were direct-smelted. In the first two years of operation a good deal of the tailing loss was caused by the oxidized content of the ores milled. Much of the ore in the transition zones between the oxides and sulphides was not mined. The ores now being milled are clean, hard sulphides in a limestone gangue, with only occasional contamination of oxides. The lead and zinc sulphides are of coarse structure and are freed even above flotation sizes. The galena is usually "steel" colored, easily and quickly floated. When there is any oxidation, it is usually on the coarsest crystals. The zinc minerals vary a good deal in color; a resin sphalerite predominates but there are varying shades of brown marmatites. On an average, the zinc sulphides contain 64 per cent zinc. The only common copper mineral is chalcopy-rite. Little is known of the occurrence of gold and silver. Waste minerals are mainly limestone and pyrite, both of which are barren. The ores vary from 20 to 35 per cent pyrite. Mill heads for the year 1940 and the first eight months of 1941 are given in Table I.

Jan 1, 1943

By Irving M. Symonds

COMPAÑIA Minera de Peñoles, S. A., at its Avalos unit operates a lead-zinc concentrator having a capacity of about 600 short tons per day. Lead and zinc concentrates are made by flotation methods. The concentrator is at Terminal de Providencia, in the state of Zacatecas, some 70 miles south of Saltillo, Coahuila. The Peñoles-Avalos railroad operating between the plant and Estacion Avalos, a distance of 6 miles, makes connections with the Coahuila and Zacatecas railroad, which in turn connects with the Nacionales de Mexico at Saltillo. The three railroads are each of different gauge, requiring the transfer of all supplies and concentrates at each junction. The mill operates on company ores, on ores from leased mines, and as a custom mill. The custom business is very small. The lead concentrates are shipped to company smelters at Monterrey, Nuevo Leon and Torreón, Coahuila. Since the European war, all zinc concentrates have been shipped to the United States. ORE TREATED The major source of ore supply is a group of four mines owned or leased by the company, some three miles south of the mill in the mountains, from which the ore is delivered to the mill by a gravity aerial tramway. Custom ore comes in by rail. The ores occur in chimneys. The upper levels contained oxidized siliceous ores of lead, copper, silver and gold, with varying amounts of zinc. These ores were direct-smelted. In the first two years of operation a good deal of the tailing loss was caused by the oxidized content of the ores milled. Much of the ore in the transition zones between the oxides and sulphides was not mined. The ores now being milled are clean, hard sulphides in a limestone gangue, with only occasional contamination of oxides. The lead and zinc sulphides are of coarse structure and are freed even above flotation sizes. The galena is usually "steel" colored, easily and quickly floated. When there is any oxidation, it is usually on the coarsest crystals. The zinc minerals vary a good deal in color; a resin sphalerite predominates but there are varying shades of brown marmatites. On an average, the zinc sulphides contain 64 per cent zinc. The only common copper mineral is chalcopyrite. Little is known of the occurrence of gold and silver. Waste minerals are mainly limestone and pyrite, both of which are barren. The ores vary from 20 to 35 per cent pyrite. Mill heads for the year 1940 and the first eight months of 1941 are given in Table I. [ ]

Jan 1, 1942

By Gordon G. Bentle, W. P. Fishel

GREINER, Marsh, and Stoughton1 have reviewed the literature in a monograph on the iron-silicon system. The lack of agreement among the various studies may be due to the difference in the purity of materials in some cases. The results of the X-ray method indicate only a general rather than a specific limit of the y loop. The iron-titanium system was investigated by Roe and Fishel,' whose results are used in determining the iron-silicon-titanium y loop. The literature indicates that no study has been made thus far of the iron-silicon-titanium system in the y loop region. Experimental Procedure The alloys were made from Armco iron, 99.86 pct Si, and 98.5 pct Ti. The titanium contains 1.07 pct Fe. The Armco iron contains 0.01 pct C, 0.005 pct Si, 0.02 pct Mn, 0.006 pct P, 0.01 pct S, and 0.04 pct Cu. A dilatation sample of Armco iron was prepared in the same manner as were the other samples. Several dilatation runs indicated that Ac3 begins at 905°C and ends at 910°C, which compares favorably with the study of Wells, Ackley, and Mehl' employing specially purified iron. All alloys were melted in an induction furnace in Alundum crucibles and were top poured into baked core sand molds. The ingots weighed about 600 g as cast. Dilatation samples of 4 in. by % in. diam were taken from the bottom end of the ingot, from which turnings for analysis were taken. Turnings from each end of two of the samples indicated that the alloys possessed uniform silicon content. A hole was drilled halfway through each end of a 4 in, dilatation sample. A chromel-alumel thermocouple was inserted in each hole and the surrounding metal peened in to hold the thermocouple in place. Fig. 1 represents the dilatation apparatus. The heating unit is an Alundum tube wound with resistance wire; the dilatation tube is a McDanel combustion tube; the push rod is zircon; the dial gage is graduated in 0.0001 in. and was vibrated to prevent sticking. A blank run over the temperature range of interest gave no significant dilatation. The thermocouples were attached to a multiple recording micromax which indicated the temperature at each end of the sample at 35 sec intervals. A Lindberg control unit governed the rate of heating of the furnace, and lowering or raising the

Jan 1, 1957

By Dan Crackel, G. G. Ramos, Mark Heisel

INTRODUCTION Feasibility studies indicated that a cratering type stoping method was best suited to the character of the first ore block at Carr Fork. This method known as vertical crater retreat (VCR) has since been modified to a combination cratering and deck blasting using VCR drop raises for initial undercut development . The modified form retains many of the advantages of VCR while allowing high tonnage production blasts which have offset many of the disadvantages. FIRST CONCEPTS AND PREMISES Geologic Considerations The Steep Highland Boy (SHB) skarn orebody, the first of several blocks being developed, is a steeply dipping 70° to 90° limb of a syncline, with a width averaging 25 m (82 ft). The bed has a consistent east-west strike length of over 400 m (1300 ft) and extends from the surface to depths of over 1000 m (3300 ft). The footwall is highly fractured quartzite and the hanging wall grades from garneti te to limes tone and hornfe 1s. Because of the limestone in the hanging wall, the hanging wall appears more competent than the footwall. The ore is garnetite with lenses of massive sulphide and magnetite. The quartzite footwall is highly fractured not only because of the bedding but also due to the folding and intrusion of the quartz monzonite. This irregular footwall outline of some stopes in- creases the likelihood of excessive dilution. The principal ore mineral is chalcopyrite with some bornite. The garnetite ore is quite variable in terms of compressive strength and drillability. In addition to the sulphide and magnetite lenses, it is transected by clay- altered dikes and major and minor north-east faults. TABLE (1) gives the range and mean strengths of the rocks. Investigating Mining Methods Initial consideration of a suitable mining method centered around maximum safety and efficiency with minimum potential dilution. The following major methods were considered and investigated. Cut and fill mining was eliminated because of low productivity, the cost and problems associated with providing fill, and the relatively unsafe nature of the method. Sublevel caving was rejected due to the unpredictable cavability of the waste and the geometry of the ore body. Conventional sublevel or blasthole methods require excessive development, as fan and ring drills are limited to efficient drilling in the 18 to 25 m range (60 to 80 ft). Mining downdip with equipment drilling small diameter holes would have required eight separate extraction/drill horizons with crosscuts and associated excavation in the main ore block. The use of down the hole (DTH) machines cap- able of drilling 165 m (6g in) diameter holes

Jan 1, 1981

By Irving M. Symonds

COMPA[N]IA Minera de Penoles, S. A., at its Avalos unit operates a lead-zinc concentrator having a capacity of about 600 short tons per day. Lead and zinc concentrates are made by flotation methods. The concentrator is at Terminal de Providencia, in the state of Zacatecas, some 70 miles south of Saltillo, Coahuila. The Pe[n]oles-Avalos railroad operating between the plant and Estacion Avalos, a distance of 6 miles, makes connections with the Coahuila and Zacatecas railroad, which in turn connects with the Nacionales de Mexico at Saltillo. The three railroads are each of different gauge, requiring the transfer of all supplies and concentrates at each junction. The mill operates on company ores, on ores from leased mines, and as a custom mill. The custom business is very small. The lead concentrates are shipped to company smelters at Monterrey, Nuevo Leon and Torréon, Coahuila. Since the European war, all zinc concentrates have been shipped to the United States. ORE TREATED The major source of ore supply is a group of four mines owned or leased by the company, some three miles south of the mill in the mountains, from which the ore is delivered to the mill by a gravity aerial tramway. Custom ore comes in by rail. The ores occur in chimneys. The upper levels contained oxidized siliceous ores of lead, copper, silver and gold, with varying amounts of zinc. These ores were direct-smelted. In the first two years of operation a good deal of the tailing loss was caused by the oxidized content of the ores milled. Much of the ore in the transition zones between the oxides and sulphides was not mined. The ores now being milled are clean, hard sulphides in a limestone gangue, with only occasional contamination of oxides. The lead and zinc sulphides are of coarse structure and are freed even above flotation sizes. The galena is usually "steel" colored, easily and quickly floated. When there is any oxidation, it is usually on the coarsest crystals. The zinc minerals vary a good deal in color; a resin sphalerite predominates but there are varying shades of brown marmatites. On an average, the zinc sulphides contain 64 per cent zinc. The only common copper mineral is chalcopyrite. Little is known of the occurrence of gold and silver. Waste minerals are mainly limestone and pyrite, both of which are barren. The ores vary from 20 to 35 per cent pyrite. Mill heads for the year 1940 and the first eight months of 1941 are given in Table I. [ ]

Jan 1, 1942

By W. Rostoker

INTRODUCTION THE process of diffusion alloying of mixed powders offers attractive possibilities both commercially and experimentally. It avoids the fabrication difficulties arising from high alloy contents. Indeed, the process is facilitated by larger alloy additions. The direct formation of the part or test piece and the opportunity to perform machining operations under more favorable conditions are of no small importance. However, it is necessary to make only brief mention of the interesting features. As yet there have been few attempts to study this process in detail and to carry it to completion, if such is possible. It was intended not only to measure the intermediate and optimum magnetic properties of sintered alloys but to use magnetic testing itself as a means of following the progress of alloying under various conditions. Having established that alloys could be successfully synthesized by this technique, the opportunity was taken to study the magnetic properties of several alloys of iron and silicon which had hitherto been too difficult to prepare in suitable test piece form, While avoiding some of the difficulties inherent in the fabrication of alloys by orthodox methods, the diffusion alloying process introduces a few of its own. The first of these is the evaluation of the approach to homogenization. In recent years some notable contributions have been made to this question, but considerable uncertainty remains in its definition and evaluation. This work has concerned itself with further study of this problem and it is hoped that more light has been shed on it, The second of these difficulties arises from the presence of porosity. It is inevitable that in the consolidation of a loose bulk of powder, there should remain some voids unless extremely high pressures are repeatedly applied. It was therefore of importance to investigate their effect on magnetic properties. Recently this effect has been studied and certain predictions made of its behavior. It is believed that the experimental results presented here provide a sound substantiation of the theoretical treatment. The attempt has been made to synthesize five alloys of the iron-silicon system and three each of the iron-nickel and iron-cobalt systems. A series of experiments was also conducted on some of these alloys to test their susceptibility to heat treatment. Some unfortunate experiences have provided opportunity to report data on the deleterious effects of nitrogen on magnetic properties when present as a contaminant in protective atmospheres. MATERIALS, PREPARATION OF SAMPLES AND TESTING The purest materials available were employed for this work. A specially purified,

Jan 1, 1948

By M. Muskat

Calculations are reported on the differential sensitivity of the updip invasion of oil strata of varving permeability to the driving pressure differential. It is assumed that the water-oil interfaces advance with sharp fronts, or that the microscopic displacement efficiency is independent of rate and capillary pressure effects. It is found that, under such conditions, limitations of withdrawal rates will not greatly inhibit the "fingering" and bypassing tendency through high permeability strata unless the differential fluid head across the original oil column is of the order of or exceeds about 80 per cent of the driving pressure differential. In practice, such restrictions will be feasible only for oil reservoirs and aquifers of high permeability and dip, but may develop automatically under combined gas injection and water drive operations. INTRODUCTION A commonly expressed view regarding the intrusion of edge-waters into oil producing formations is that the geometry of such advance is rate sensitive. Specifically, it has been suggested that high rates of advance, stimulated by rapid withdrawals, will lead to "fingering" and an irregular type of invasion, whereas at low withdrawal rates the water encroachment will be more uniform. Two factors tend to support this view. One is the resultant effect of capillary pressure and gravity gradients in the displacement processes' involved in water intrusion, which are magnified at low rates of flow so as to improve the recovery efficiency. The other is the direct retarding effect of the rising water head as it advances upslope into the producing area. Capillary pressure forces give rise to a rate sensitivity of the oil recovery by water displacement in uniform strata as well as differential effects in non-uniform formations. These are basically independent of the effect of gravity and would also occur in horizontal beds or when the oil and water have the same density. Unfortunately, however, the fundamental equation describing the displacement process under the action of capillary pressures can be solved only by numerical or graphical procedures, and moreover the solutions are sensitive to the character of the capillary pressure and relative permeability curves.* On the other hand, the direct effect of gravity can be given a formal analytical solution if the simplifying assumption is introduced that the water advances with sharp fronts in the individual uniform strata. It depends on the absolute permeabilities of the water invaded zones and hence results in a rate sensitivity of the differential invasion in stratified media. Although a tieatment of this factor alone will not give a complete evaluation of the effect of rate on water intrusion in non-uniform pays, it should provide at least a semiquantitative measure of the sensitivity of "fingering" to withdrawal rate. Such a treatment will be presented in the following sections. GENERAL THEORY The basic element of the theory is the history of water advance updip in a uniform stratum (Fig. 1). In contrast to the assumption of constant flow rate, generally made in the analysis of displacement processes, we shall assume here that

Jan 1, 1951

By F. H. Wilson, E. W. Palmer

G. L. Bailey (British Non-Ferrous Metals Research Association, London, England)—I was glad to see this further work on the structure and properties of the Cu-Ni-Fe alloys of low nickel content in which we have been so interested in the United Kingdom since before the war." The authors' data on the variation in solubility of iron in both 5 and 10 pct Ni alloys with temperature is based on more detailed observations than we have made but is generally in line with our own work. The difficulty in these matters is in the identification of the structures obtained. The precipitation of the second phase which we presume to be the a' solid solution, richer in nickel and iron, from the a solution with which it is in equilibrium occurs in such a fine state of division that its resolution by ordinary micro-graphic methods is impossible in the early stages. We have published some electron micrographs which illustrate the effects observed more clearly but we agree with the authors when they say that dark staining characteristics when the alloys are subjected to sea-water corrosion are more sensitive in detecting the presence of the a' phase than is the microscope. After taking this point into consideration, however, I confess to some difficulty in understanding Fig. 4. I can only assume that the precipitates visible at such a low magnification as 150 diam in these relatively coarse forms are produced from iron-rich areas of the initial solid solution due to inadequate homogenization. If this is so I find it difficult to accept the authors' contention that such local variations in iron concentration as are capable of giving the heavy precipitates shown in Fig. 4 do not in fact materially affect the solvus surfaces of their equilibrium diagrams. I share the authors' enthusiasm about the resistance to corrosion of these alloys by seawater but I am not fully in agreement with them on the vexing question of the best iron content for these alloys. In Fig. 3 of ref. 8, we give many results showing that the resistance of these alloys to impingement attack in the Jet Test increases as the iron content rises to 2 pct. With higher iron contents pitting at shielded areas is likely to occur. Admittedly the addition of 0.75 pct Fe produces a large improvement in corrosion resistance compared with a pure 90/10 Cu-Ni alloy, but the further improvement on raising the iron to 2 pct is substantial. We recommend from 1.5 to 2 pct Fe as the desirable range from the point of view of corrosion resistance. While it is true that British practice generally uses a hard tube, the corrosion resistance of the 10 pct Ni alloys has in our work been little affected by the structural condition. Although the annealed alloys blacken in seawater, this effect seems to be superficial and not to be accompanied by any real decrease in

Jan 1, 1953

By G. R. Rubly, H. J. Steele

LOCATION AND HISTORY THE San Manuel property is in townships 8S and 9S, range 16E, Gila and Salt River Base and Meridan, State of Arizona. This area is in the Old Hat mining district, southern Pinal County, and is about 3;2 miles southwest of the town of Mammoth on the San Pedro River and one mile south of the Mammoth mine at Tiger, Arizona. The property consists of over 150 contiguous lode claims. The Old Hat district was prospected prior to the Civil War, but there was little or no production until 1881.1 The chief producers have been the Mammoth and Mohawk mines, now consolidated and operating as the St. Anthony Mining and Development Co., Ltd. Production to 1936 was $5,200,000, of which 83 pet was gold.2 Since 1940 the production has been chiefly lead and zinc, and some molybdenum and vanadium. There are a few small properties in the vicinity that have produced very minor tonnages of copper ore. In the San Manuel group there are claims which have been held continuously from 1906 to the present time, and at least two churn-drill holes were put down on or near the outcrop in 1917. No logs for these holes are available, but it is assumed that the grade of copper encountered was not sufficient to encourage further exploration. A small amount of ore has been shipped from open cuts on the San Manuel outcrop area, but there is no record of the tonnage or grade. It is estimated that not more than 5o tons were mined. These cuts, plus a few shallow shafts and some short adits indicate limited and unenthusiastic prospecting at San Manuel. In 1942, through the efforts of James M. Douglas, R. B. Giffin, Victor Erickson, and Henry W. Nichols, owners of the San Manuel group, the Reconstruction Finance Corporation and War Production Board authorized the United States Geological Survey to investigate the property, and by their recommendation, the United States Bureau of Mines was authorized to put down a limited number of churn-drill holes. The Bureau of Mines carried on drilling from November 1943 to February 1945. Seventeen holes were drilled, varying from 305 to 1990 ft in depth. The property was brought to the attention of Magma Copper Co. in June I944 and an option agreement was made with the owners. Subsequently, a group of claims lying north of the original group and held by the Apex Lead Vanadium Mining Corp., and a group to the east held by the Quarelli family, were optioned. A drilling program was laid out to conform to the Bureau of Mines pattern, and drilling started in December 1944. San Manuel Copper Corp. was incorporated September 1945, and has carried on the exploration program to the present time. GEOLOGY General The mineralized outcrop, chief copper mineral of which is chrysocolla, is a tri-

Jan 1, 1947

By B. Blumenthal

THE present investigation was planned as a survey of the lead-rich portion of the ternary lead-antimony-silver system by thermal analysis. Since, however, a rigorous application of the conventional thermal analytical method is time consuming, an attempt was made to speed up the investigation by reducing the time required for a single thermal analysis. This was done by increasing the rate of cooling to 12° to 18°C. per minute. Since such a rate does not permit even an approach to equilibrium conditions, the melt was stirred vigorously by a stirrer operating at the high rate of 665 r.p.m. This proved to be effective in obtaining cooling curves with distinct points of arrest and of excellent reproducibility, which satisfactorily compare with those obtained at a rate of 1° to 2°C. per min. with or without slow stirring (Fig. 1). By this method the lead-rich end of the lead-antimony system and a series of ternary alloys in sections parallel to the lead-antimony side of the ternary system were investigated and it was observed that the two branches of the' liquidus curve of the .binary alloys did not intersect at the eutectic temperature. An equivalent effect was observed in the ternary system. The eutectic temperature of the binary lead-antimony system was found to be 252.0°C., which confirms the recent investigation by Pellini and Rhines,1 who determined the eutectic temperature to be 251.5°C. The observation that the curves of primary crystallization of the lead-antimony system do not intersect at the eutectic temperature was previously made by Dean.2 Dean explains the phenomenon by assuming the existence of a compound Sb4Pb. He felt that super-cooling was not the cause of the phenomena because he was unable to influence them by inoculation. The X-ray investigation by Solomon and Morris-Jones,3. the metallographic investigations by Stead,4 Charpy,5 Gontermann,6 and Dean, Zickrick and Nix,7 and the numerous investigations of physical properties, definitely disprove the occurrence of any compound. The work of Dean was not confirmed by Broniewski and Sliwoski,8 whose experiments did not show any irregularity and who report a eutectic composition of 13 per cent antimony and a eutectic temperature of 250° to 252°C. at a rate of cooling of about 6°C. per min. Abel, Redlich and Adler9 then report a eutectic composition of 12.1 per cent upon reviewing the previous, publications and adding a few of their own cooling curves. In 1934 Quadrat and Jiriste10 found from careful analyses of the bottom portion of slowly cooled hypereutectic melts that the eutectic contains only 11,4 to 11.5 per cent antimony. (Previous analyses by Stead4 in 1881 gave 13 per cent:) Weaver," however, reported in 1935 that cooling curves indi-

Jan 1, 1943

By O. J. C. Runnalls, L. M. Pidgeon

J. M. Blocher, Jr. and I. E. Campbell (Battelle Memorial Institute, Columbus, Ohio)—Since the de Boer-Van Arkel process for making titanium metal involves a number of steps in a fairly compact unit, it is difficult to determine simply which of the steps is rate controlling. In any statement as to which step constitutes the rate-controlling process, qualifications appear to be in order. It is possible to design a reaction bulb in which any one of a number of steps is made to be controlling. I—With the filament removed some distance from the crude, as in the case of the authors' experiments, the interdiffusion of iodine and iodide may be controlling. 2—If, as is usually done, the crude metal is placed in a perforated cylindrical basket, or as a briquetted mass, in close proximity to the filament, the rate of deposition is increased (we obtained rates of deposition 5 to 10 times those cited in the authors' paper), and another rate-limiting factor, such as the reactivity of the crude, may take over. In this regard, we have noticed radically different rates of deposition with different crudes, and with crudes in various stages of exhaustion. 3—With a very reactive crude metal and with optimum practical geometry, still another process may be controlling. It is felt that this is a diffusion process in the immediate vicinity of the filament involving the fundamentally adverse situation of a net flow of particles away from the filament. The separate experiments on the reactivity of iodine with titanium are interesting but somewhat inconclusive. Data is still needed on the partial pressure of iodine in an operating decomposition bulb. A knowledge of the gradient of iodine partial pressure from the crude to the filament would be particularly enlightening. Optical absorption may be a useful technique here. Accurate measurements of the total pressure within a decomposition bulb under various conditions would be quite revealing. Preliminary measurements have been made at Battelle in following this line of attack. It is interesting to note that the authors' data on the temperature dependence of deposition rate indicate that the overall rate is not controlled by the kinetics of the decomposition reaction at the filament: TiI1 ? Ti + 4I Any reasonable estimate of the activation energy of this reaction would, if its kinetics were controlling, dictate a much greater temperature dependence than is observed here. The authors apparently attribute the drop in deposition rate (eventually to zero) with increased TiI4 pressure solely to a decrease in diffusion rate. However, there is an equilibrium factor involved here that must not be overlooked. As the partial pressure of TiI4 is increased, a point is reached where, due to the competing reaction of the tetraiodide with titanium to form lower iodides, the equilibrium partial pressure of titanium is reduced to the point that it equals the vapor pressure of titanium at the filament temperature and the deposition rate falls to zero. This effect would

Jan 1, 1953

By R. A. Perry

A speiss is an artificial arsenide, sometimes an antimonide, formed in lead smelting, smelting of oxide copper ores, and in some lead-refining operations. The production of speiss is closely allied with the amount of arsenic and metallic iron in the blast-furnace charge, while dross is produced mostly from the copper and sulphur, with varying amounts of antimony, arsenic and nickel. Most speiss is essentially an iron arsenide containing some sulphur, copper and nickel, if these elements are present in the furnace. The recent introduction of the soda treatment of lead drosses has produced a speiss high in copper. Speiss is not miscible to any extent with molten copper, lead, matte or slag. Miscibility increases with temperature. This property of the speiss is clarified in the latter part of this paper. Most speisses are produced in conjunction with matte and their sulphur content points to the solubility of matte in speiss. . Some plants have insufficient speiss to warrant separate treatment. When arsenic is high in the blast-furllace charge, there may be sufficient speiss to tap separately from the first settler. Arsenic From the foregoing, it is obvious that a study of the treatment of speiss would not ,be complete without consideration of arsenic. Inasmuch as perhaps go per cent of the blast-furnace feed may be sinter, a definite knowledge of the properties of arsenical ores and compounds that go in to the roaster and sinter feeds is of value. Lcad smelters obtain their arsenic from ores and concentrates, as well as from flue dusts shipped from other plants, particularly copper smelters. The percentage of arsenic in ores is usually low, although occasional lots of high arsenical products are smelted. These crude ores may be sulphides, as arsenopyrite; or oxides like scoiodite, which carry gold or lead minerals. The small amount of arsenic in the original ores received is greatly increased by a circulating load of arsenic in secondary products at are resmelted for their lead or precious metals. More important than the arsenic present directly in the concentrates treated is that in fumes and dusts that may originate in the blast furnace or sinter plant of the lead smelter, or may come from a copper smelter as lead-bearing converter fume or roaster dust. Thus the lead smelter not only must treat its own arsenic but is compelled to handie that from some copper and perhaps other lead plants. Where copper and lead plants exchange products, each plant may be forced to re-treat part of the arsenic it has shipped ,outside its own confines. Speiss from the lead blast furnace contains chiefly iron and arsenic with some lead, copper and sulphur and often appreciable amounts of gold and silver. If its copper content is sufficient this speiss may be sent to the copper smelter where usually it is treated in the converter and the copper is separated as blister. Much of the arsenic and most of the lead are recovered as converter fumes

Jan 1, 1944

By R. Schuhmann

As a response to rapidly growing specialization in various branches of metallurgy, it is proposed that undergraduate education in metallurgical engineering should be built up around four principal scientific themes: 1—thermodynamics, 2—structure, 3—mechanics, and 4-—rate processes. THE following quotation from a recent article by von Bertalanffyl describes very well the situation which today challenges curriculum designers in all branches of science and engineering: "Modern scientific education is presented with a well known dilemma. The amount of facts in modern science, and in any of its smallest branches, is enormous. Life in general, and the academic curriculum in particular, is short. The abundance of factual data, as well as the intricacy of modern scientific techniques, experimental and theoretical, necessitates utmost specialization. This specialization, unavoidable though it is, involves serious danger for both the education of the scientist and the social function of science. "In so far as the advancement of science is concerned, history shows that interconnection of different fields and problems is a most important basis of progress. Many of the paramount achievements of science arose on borderlines, and from the synthesis of formerly separate fields . . ." Specialization in subfields of metallurgy has become a serious educational problem only in about the last decade. The growth in specialization, almost as a necessity, has paralleled the rapid growth in metallurgical knowledge during this period. Moreover, in planning future educational policies, the educator must be concerned not only with the rate of increase in metallurgical knowledge and with the concomitant rate of increase in specialization, but also with the second derivatives, that is, with the rates of increase of the rates of increase. These second derivatives are positive and large; the growths being dealt with are self-catalyzing, or like a chain reaction. As a measure of specialization, the length of the list of different kinds of metallurgies can be considered, the kinds of metallurgy which represent one person's particular interests and those of other practicing metallurgists. To start with, there are physical metallurgy, process metallurgy, and mineral dressing, then mechanical metallurgy, metal processing, foundry metallurgy, corrosion, solid state physics, high temperature metallurgy, welding, powder metallurgy, nuclear metallurgy, etc. Each of these fields is growing so rapidly that any one metallurgist can hope at best to keep up to date in only one or two. What is the impact of all these "metallurgies" on metallurgical education and metallurgical curricula? In answering this question, it can be said, first, that educators have resisted fairly well the temptations to split up metallurgy, with different curricula, different options, degrees with different labels, and the like—degrees are still given in plain Metallurgy and Metallurgical Engineering. In other ways, though, the pressures of specialization have had noticeable effects. There is a tendency to think of these "metallurgies" as the important subdivisions of Metallurgical Engineering and to work up

Jan 1, 1956

By M. Muskat

Calculations are reported on the differential sensitivity of the updip invasion of oil strata of varving permeability to the driving pressure differential. It is assumed that the water-oil interfaces advance with sharp fronts, or that the microscopic displacement efficiency is independent of rate and capillary pressure effects. It is found that, under such conditions, limitations of withdrawal rates will not greatly inhibit the "fingering" and bypassing tendency through high permeability strata unless the differential fluid head across the original oil column is of the order of or exceeds about 80 per cent of the driving pressure differential. In practice, such restrictions will be feasible only for oil reservoirs and aquifers of high permeability and dip, but may develop automatically under combined gas injection and water drive operations. INTRODUCTION A commonly expressed view regarding the intrusion of edge-waters into oil producing formations is that the geometry of such advance is rate sensitive. Specifically, it has been suggested that high rates of advance, stimulated by rapid withdrawals, will lead to "fingering" and an irregular type of invasion, whereas at low withdrawal rates the water encroachment will be more uniform. Two factors tend to support this view. One is the resultant effect of capillary pressure and gravity gradients in the displacement processes' involved in water intrusion, which are magnified at low rates of flow so as to improve the recovery efficiency. The other is the direct retarding effect of the rising water head as it advances upslope into the producing area. Capillary pressure forces give rise to a rate sensitivity of the oil recovery by water displacement in uniform strata as well as differential effects in non-uniform formations. These are basically independent of the effect of gravity and would also occur in horizontal beds or when the oil and water have the same density. Unfortunately, however, the fundamental equation describing the displacement process under the action of capillary pressures can be solved only by numerical or graphical procedures, and moreover the solutions are sensitive to the character of the capillary pressure and relative permeability curves.* On the other hand, the direct effect of gravity can be given a formal analytical solution if the simplifying assumption is introduced that the water advances with sharp fronts in the individual uniform strata. It depends on the absolute permeabilities of the water invaded zones and hence results in a rate sensitivity of the differential invasion in stratified media. Although a tieatment of this factor alone will not give a complete evaluation of the effect of rate on water intrusion in non-uniform pays, it should provide at least a semiquantitative measure of the sensitivity of "fingering" to withdrawal rate. Such a treatment will be presented in the following sections. GENERAL THEORY The basic element of the theory is the history of water advance updip in a uniform stratum (Fig. 1). In contrast to the assumption of constant flow rate, generally made in the analysis of displacement processes, we shall assume here that

Jan 1, 1951