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By Alan Bauer

DRILLING CONSIDERATIONS In considering blasting it is necessary to consider the drilling and explosives since one is generally concerned with the total cost of muck of a certain size in the pit or through the crusher. To get a current idea of the drilling situation in open pit mines plotted in Fig. 1 are the drilling costs per ton of material vs. hole diameter for rotary drill holes in large limestone, iron ore and taconite operations. The exception is the 2-in. diam hole which was drilled with a percussion drill in limestone. Each curve in Fig. 1 represents a different operation and the data cover many months of production drilling. The costs are total operating and maintenance and do not include machine depreciation. As the hole size is increased so are the machine size and the investment. Providing the tonnage is available to be drilled, then as the machine size goes up so does the productivity-markedly-and this same shape of curve applies. In some instances it is even steeper. The interesting thing to note is that in each case studied there is a substantial drop-off in cost/ton as the hole size is increased. This is true for the softest material considered, limestone, through to the hardest, taconite. How has this come about? In going from 10-in. to 123-in. diam holes, the powder factors have generally stayed about the same and the same type of muck has been produced. To date this has been mainly in the softer materials but it has also been steadily taking hold in the harder ones. On this basis, then, patterns are generally expanded as the ratio of the hole diameters or close to it, if the explosive type is kept the same. In the harder rocks the cost per foot of hole has increased somewhat so that the overall reduction in drilling cost per ton is about 25 pct. In somewhat weaker rocks of about 25,000 psi compressional strength the drilling cost per

Jan 1, 1968

By N. De Nevers

A calculation method has been developed for carbonated water flooding. This method takes into account the effects of oil viscosity reduction and oil swelling, due to carbon dioxide transferred to the reservoir oil from the carbonated flood water. It shows the effect of changes in carbonation pressure and carbonated water slug size. The method is based on a Buckley-Leverett-type linear flow model. The mathematical approach is similar to that developed by Welge, et al, for enriched gas drives. However, it contains a very important advance over the previous papers in its solution to the problem of injection of a "slug" of carbonated water rather than continuous injection of fluid of constant composition. The method also shows the chromatographic nature of the transport of Co 2 in a carbonated water flood. Sample calculations indicate that viscosity reduction is the most important source of incremental oil recovery. Swelling contributes to a lesser extent. Raising the carbonation pressure increases recovery, but this effect diminishes as pressure is increased. increasing the slug size also increases recovery, but again this effect diminishes as slug size is increased. INTRODUCTION In recent years there has been considerable interest in carbonated water flooding as a secondary recovery method. Several carbonated waterflood field tests are now in progress.1'3 Yet there is no published method for predicting the results of a carbonated water flood. This paper presents a method for predicting the oil recovery for ; carbonated water flood. In a carbonated water flood. a carbonated water slug is injected into the reservoir. Then this slug is driven forward by injecting plain water behind it. The field operator must choose the carbonated water slug size and the CO2:water ratio in the slug. The calculation method presented here shows the effects of both slug size and CO2:water ratio on oil recovery. The calculation assumes that the addition of carbon dioxide to flood water increases the oil recovery by two mechanisms: 1. Carbon dioxide transfers from the flood water to the oil, thereby reducing the viscosity of the oil. At the lower viscosity, the oil flows more readily and is more easily swept out by flood water. 2. The carbon dioxide which transfers to the oil phase causes the oil phase to swell. Assume that the residual oil saturation (volume per cent of pore space) is the same whether the oil is carbonated or not. Then the same volume will contain less stock tank oil if it is carbonated, due to oil swelling. The plain water driving the carbonated water slug forward will strip the CO2 out of this residual oil., causing this oil to shrink. This swelling-followed-by-shrinking leaves behind a lower residual oil saturation than would have been left behind by a plain water flood. Since some oils swell to almost twice their original volume at reasonable CO2 pressures, this effect may be large. Two additional benefits sometimes claimed for carbonated water flooding are: 1. Adding CO2 to flood water greatly increases the water injectivity in some cases.1 (Injectivity = BPD of water injected/ft of sand x differential bottom-hole pressure, psi.) CO2 forms a weak acid in water; injecting carbonated water is, therefore, somewhat like acid treating. If a formation responds to acid treating, it will probably have a higher injectivity for carbonated water than for plain water. Although the increased injectivity increases the profitability of a carbonated water flood over a plain water flood, it does not change the production curve based on total fluid injected. Therefore, the method presented here does not show any effect of increased injectivity. 2. It is claimed in one patent4 that carbon dioxide will react with some constituents of the oil to form detergents. These detergents are expected to increase the oil recovery. There is little data available to support this idea. The calculation method presented here takes no credit for extra oil recovery due to the formation of any such detergents.

Jan 1, 1965

By Arthur Knapp

Oil-well depletion curves, to be of value, should show when a well or lease may no longer be operated at a profit. The difference, at any time, between the total expenditures and the total income of a lease or well may be called the lease status. Plotting this lease status against time will give a curve subject to more accurate and different interpretations than the barrels-time curves. According to the hypothetical barrels-time curves shown in Fig. 1, well A, at the end of 16 mo., is producing twice as much oil as well B and will continue to produce for another year whereas well B will cease producing in about 6 months. Data fob Lease Status-time or Dollars-timb Curve Time Lease Months Status Lease purchased for $3000.............................. 0 — $ 3,000 No expenses chargeable to lease for 3 mo................. 2 — 3,000 Well A is started; cost of drilling for month is $16,000..... 3 — 19,000 Well is completed at additional cost of $10,000............ 4 - 29,000 Well A is brought in and flows 10,000 bbl. first month (we Fig. 1). Necessary to invest in tanks, boilers, pipe lines, etc.; difference between expenditures and receipts gives profit for month of $5,000............................ 5 — 24,000 Investment is small, cost of operating well A is small, so profits are $15,000................................... 6 — 9,000 Well ceases to flow so there is additional investment for pumping equipment and additional operating expense; net earnings from 6,000 bbl. of oil produced is $4,000. 7 ... Lease operation nor becomes normal and curve becomes smooth........................................... 8 — 500 9 2,000 10 4,500 11 6,000 12 7,700 13 8,700 14 9,000 15 9,500 16 10,000 A hypothetical lease status-time, or dollars-time, curve of this lease is shown in Fig. 2. At zero time, the lease is purchased for $3000, which is plotted below the zero dollar line, All subsequent entries are plotted

Jan 1, 1921

By John Crawford

MUCH has been written of late regarding the flotation of coal as a means of reclaiming the valuable portion of the fines encountered in nearly all methods of coal preparation. Whether the process be wet or dry, whether the dust be sent through the entire process or removed prior to the cleaning by some such method as screening or aspiration, one of the final products consists of a considerable proportion of -48-mesh material. The percentage of this -48-mesh material depends upon the mining method, transportation, storage, and method of preparation. The ton-nage of this dust material ranges from 1 to 10 per cent of the total output of the cleaning plants. Four methods of disposal are available for this coal: 1. Disposal with the refuse from the plant. 2. Addition, after being reclaimed from the wash water, or dust collectors, without cleaning to the larger sizes. 3. Separate disposal as a pulverized fuel. 4. Cleaning so that addition to the larger sizes benefits the product as a whole. It is also true that flotation in one form or another is the only known way to effectively clean this material. While some processes do a reason-able cleaning job down to and including +100 mesh, by far the greater-majority stop at or short of the +48-mesh size.

Jan 1, 1935

By B. Fagerberg, P. H. Fahlstrom

Crushing and grinding practice in Sweden follows closely the international pattern. Certain special circumstances, however, have had an influence on its development. Most mines are worked underground. These mines are either quite small or very large. Sulfide ores are commonly treated by custom milling and, apart from the cement industry, the rock species treated are hard and abrasive. Another important factor is the increasingly strict requirements placed on the mechanical condition of different products, especially lump ores and coarse iron-ore concentrates. Increasing requirements are being placed on the concentrate grade to suit the new steel processes. As a result, iron ore beneficiation has expanded considerably for the production of fine pelletizing concentrates. This applies especially to magnetite ores in the intermediate phosphorus range 0.1-1% P. In 1969, about 5.5 million tons of pellets will be manufactured. It should be pointed out, however, that fairly large quantities of coarse products are still being made at mills where the right conditions are available. Crushing and grinding is also of great importance in the production of rich concentrates at high recovery from sulfide ores. In fact, a large part of the development work on the concentration of sulfide ores has been devoted to the crushing and grinding processes. Boliden has played an important role in this connection.

Jan 10, 1969

By C. F. Floe, M. Cohen, M. B. Bever, V. G. Paranjpe

P. Coheur and L. Habraken—We read this paper with great interest and are glad to congratulate the authors for their valuable work, supplying an important contribution to the mechanism of tempering on the carbides in vanadium steels. We are in a good position to appreciate this work since we have been studying, for more than a year, Cr-Mo steels of a composition similar, but less highly alloyed (namely 0.1 pct C, 3 pct Cr, 1 pct Mo). Our results are quite in concordance with the authors', however, we wish to point out that it is very interesting to use equally the electron microscope in order to observe the variations of microstructure in steels. We have studied simultaneously the evolution of the carbides in situ with the electron microscope, and, after extraction, again with the electron microscope, and then with X-rays. The first results which we have obtained have been communicated at the Congress of Delft (July 1949) and at the "Journees de la Metallurgie" in Paris (October 1949). These may be summarized as follows: After tempering with varying either the tempering temperatures or the tempering times, the carbides show two evolutions. The first one is connected to the carbides existing in the steels, principally in the boundaries of the grains. For some groups of steels these carbides may coalesce and for other groups they may

Jan 1, 1951

By N. J. Grant, D. S. Bloom

P. Coheur and L. Habraken—We read this paper with great interest and are glad to congratulate the authors for their valuable work, supplying an important contribution to the mechanism of tempering on the carbides in vanadium steels. We are in a good position to appreciate this work since we have been studying, for more than a year, Cr-Mo steels of a composition similar, but less highly alloyed (namely 0.1 pct C, 3 pct Cr, 1 pct Mo). Our results are quite in concordance with the authors', however, we wish to point out that it is very interesting to use equally the electron microscope in order to observe the variations of microstructure in steels. We have studied simultaneously the evolution of the carbides in situ with the electron microscope, and, after extraction, again with the electron microscope, and then with X-rays. The first results which we have obtained have been communicated at the Congress of Delft (July 1949) and at the "Journees de la Metallurgie" in Paris (October 1949). These may be summarized as follows: After tempering with varying either the tempering temperatures or the tempering times, the carbides show two evolutions. The first one is connected to the carbides existing in the steels, principally in the boundaries of the grains. For some groups of steels these carbides may coalesce and for other groups they may

Jan 1, 1951

By J. S. Kirkaldy, R. J. Brigham

AS part of a program to investigate the diffusive properties of dilute ternary austenites we have made a determination of the effect of chromium on the activity of carbon in ? iron. Samples of pure iron and Fe-Cr alloys were simultaneously equilibrated at 1000°C with atmospheres of controlled CO/CO2 ratio following the procedures of Darken and Gurry 1 and smith.' The 0.020 in. thick samples were analysed for carbon by microcombustion analyses3 to yield a set of isoacti-vity curves. The latter were converted to activity coefficient (standard state at infinite dilution) plots by combination with Smith's data2 for the activity of carbon in pure iron. Table I shows the compositions of the base alloys used while Fig. 1 shows the experimental results superimposed on a set of curves generated by the relation In?C=6.9NC- 10.7 Ne In the notation of wagner4 the interaction parameter is the second coefficient on the right, Sgr = - 10.7 This can be compared with a rather inaccurate value deduced from the transient equilibrium diffusion data of Kirkaldy et al.' as The authors are indebted to the American Iron and Steel Institute for financial support. This material is condensed from a B.Sc. Thesis submitted to Mc-Master University by R.J.B.

Jan 1, 1963

By H. Landsberg

Biological as well as geological research has made very successful use of the qualities that the physicists have detected in radioactive substances. Outstanding examples for the vast new fields opened in this part of the border-land between the disciplines of geology and physics are the "radio thermal geology" [July, 1909, see 1 of "References" at end of paper] and all that is connected with the use of the radioactive disintegration clock for the age-determination of rocks and minerals [2]. In structural geology, not unlike to recent bi-ological uses of radioactive material, their "tracer" properties were helpful. Changes in Radon concentra-tion in soil-air, especially accumulations, led to hidden crevices and fault-zones. High contents of Radon in spring-water gave clues as to the types of rocks they had flowed through [3, 4). One specific application of the small admixtures of radioactive material, however, has only lately found some atten-tion and that is their use in linking beds of sedi-mentary strata otherwise only poorly identified be-cause of the lack of fossils or other characteristic properties. To be useful for this purpose, two con-ditions have to be fulfilled: (1) The amount of radioactive material per unit-weight of rock in a given horizon should be uniform over a large area; (2) this same amount should change fairly rapidly in the vertical succession of layers.

Jan 1, 1940

By W. J. Reagan

MANY factors enter into the manufacture of basic open-hearth steel of high quality. Perhaps the two most important are temperature and the iron oxide content of the metal. If we can control these two factors we can essentially control basic open-hearth practice. SOURCE AND EFFECT OF IRON OXIDE Earlier investigators, especially Herty and his associates, have shown that iron oxide is introduced into the open-hearth furnace in four ways:1 1. - By oxidation of the scrap by furnace gases. 2. By decomposition of the limestone. 3. By oxidation of the iron oxide in the slag by furnace gases. 4. By direct addition of iron ore to the charge. We also know that the speed of operation of an open-hearth furnace depends, for a given charge and given combustion conditions, on the rate at which iron oxide will diffuse from the slag into the metal. The rate of diffusion depends upon a number of variables, such as iron oxide content of the slag, slag viscosity, etc., which also depend upon the amount of iron oxide in the metal, amount of carbon present, temperature, and so forth. For a given carbon and a given temperature, the iron oxide content of the metal is in proportion to the iron oxide content of the slag. This fact can be easily verified by analysis of slag samples taken as described by Herty.2 It is preferable to take these samples just before deoxidation. In killing the steel samples with aluminum it is desirable to use aluminum rod of 99 per cent purity; ordinary commercial aluminum rod with a purity of approximately 92 per cent is not satisfactory. In drilling these samples it is also essential to take the largest amount of drillings possible. This gives more accurate results because it eliminates spotty segregation of Al203.

Jan 1, 1932

By J. L. Stuck

Geological investigation and research have contributed greatly in making industrial minerals the basis of an important industry in the state. North Carolina contains a wide variety of industrial minerals and rock. Mica, feldspar, kaolin, halloysite, talc, pyrophyllite, silli-manite, and spodumene are used to illustrate the progress being made. IN a previous paper1 an attempt was made to indicate the importance of industrial minerals in North Carolina and the wide variety of such materials present. The present paper is concerned with geological investigation and research which have made industrial minerals the basis of an important industry in the state. Geological mapping has gone through three stages in North Carolina during the present century. The first stage is represented by excellent reports of which Corundum and the Peridotites of Western North Carolina,2 Volume I, now a classic, is representative. In this report, a geologic map of the western third of the state is shown on a scale of 10 miles to the inch. The next stage is represented by folios" of the U. S. Geological Survey published between 1902 and 1932. Most of these contained 30 min quadrangle maps on a scale of 2 miles to the inch. The third step is represented by reports prepared during the past 10 years which contain geological maps4 on scales varying from 500 ft to 1 mile to the inch, while many mine maps have been prepared on scales varying from 20 to 150 ft to the inch. As the scale on which geological mapping has been done has decreased, the amount of information secured has increased. Pratt and Lewis did excellent work on the peridotites of western North Carolina, but their maps lacked details. Keith and others added

Jan 1, 1952

J. S. UNGER, ? Pittsburgh, Pa. (written discussion ?).-Firebricks intended for, the same purpose, but supplied by different manufacturers, may be of entirely different clays, contain different proportions of flint, calcined and plastic clays; the particles may vary widely in size; the water used to make the brick will vary; the pressure in molding will vary, depend-ing on whether the brick is hand made or power pressed; and the degree of burning in the same kiln will differ. These variables affect the melting point and the strength of the brick when heated. An important property, of a firebrick is its ability to resist heat and, at the same time, weight or load without serious deformation. The soft-ening point and the melting point of a firebrick may be several hundred degrees apart, and two bricks may show considerable difference in their softening points, but the melting points may be approximately the same. Bricks are not usually employed at temperatures close to their melting points. If they must withstand very high temperatures, the firebrick is discarded and a brick of more refractory material is used. Under these conditions' it is doubtful whether the determination of the melting point of a brick has much practical value. If the determination of the melting point is necessary, the test should he made on a portion of the original brick and not on a specially prepared sample. A small triangular pyramid with a base about 1 1/2 in. and 3 in. high can be sawed from the corner of the brick with a thin-bladed car-borundum wheel, without injuring or destroying the size of particles, the bond, or degree of burning of the original brick. This specimen can then he compared with standard Seger cones or tested by any other method desired.

Jan 12, 1919

By W. B. Morrison

Anderson, King, and Spreadborough present detailed evidence to show what ~aldwin~' has already pointed out, that, over a relatively small grain-size range (Ad"1/2 ^ 10 mm-'I2, d is average grain diameter), yield point data can fit a number of relationships. Part of the difficulty in obtaining data which reflect only the effect of change in grain size on yielding arises from the fact that in varying the grain size, even though great care is taken, other structural changes are almost certain to occur. In iron alloys, these changes may consist of variations in subgrain size, grain boundary ledge density, and degree of carbon and nitrogen segregation at grain boundaries, all of which are difficult to detect and which may affect yielding, primarily through their effect on dislocation generation. Because of the inherent inaccuracy associated with yield point measurements there is little point in using relatively complex equations to fit data, as was done by Anderson et mnl., rather than the simpler, widely used Hall-Petch equation. In compiling their table of data, it is surprising that they did not include results from certain low-carbon steels,31 in which, as illustrated in Fig. 2, the grain-size range is very much larger than in their Armco Iron. The very fine grains in these steels were obtained by a thermomechanical process. Examination by electron microscopy showed that the grains were separated by high-angle boundarie and contained only an occasional subboundary. The data from these steels obeyed the Hall-Petch equation, and it was shown quite conclusively that they did not fit a d-l or (1-lJ3 relationship. Obviously, a much wider range in grain size than used by Anderson et al. is desirable if we are to determine the true relation between lower yield stress and grain size.

Jan 1, 1969

By N. J. Grant, R. Nordheim

An extensive study was made of the aging characteristics of alloys based on the 80 pct Ni-20 pct Cr composition hardened with aluminum and/or titanium, each up to 4 pct. Aging was followed by means of hardness and hot electrical resistance measurements as well as by X-ray and microscopy. Stress rupture tests at 1500°F were utilized as a check on the predicted behavior. THE titanium and aluminum hardened Ni-Cr alloys, exemplified by Nimonic 80 and Inconel X, constitute one of the more important groups of alloys developed to meet the demand for materials retaining their strength at elevated temperatures. For service in the temperature range 1200" to 1500°F, these alloys offer high creep resistance. With increasing service temperature, however, the strength of the simpler Ni-Cr base alloys falls off rapidly so that above 1500°F there is a significant loss of strength. The present investigation was undertaken with the hope that a better understanding of the factors controlling the precipitation hardening of these alloys would make it possible to increase the useful service temperature range. Primarily this investigation involved the study of the effects of titanium and aluminum on the hardening and the subsequent softening at elevated temperatures. The titanium and aluminum contents were each varied between 0 and 4 pct by weight at a constant nickel to chromium weight ratio of about 4:1. (Except when otherwise stated, all compositions are expressed on a weight basis.) The major part of the investigation was confined to alloys with less than 0.06 pct C. Recently several papers dealing with the identity of the microconstituents in the titanium and aluminum hardened Ni-Cr alloys have been published. Using X-ray analysis of the residues from anodic dissolution, Rosenbauml was only able to identify carbides and nitrides in Nimonic 80 and Inconel X. However, since Rosenbaum worked with alloys in the hot rolled rather than in the aged condition, his results are inconclusive. Recently Hignett' reported that the hardening of Nimonic 80 was due to the controlled precipitation of Ni,(TiAl) having the cubic Ni3A1 structure. Taylor and Floydv-" published the results of an investigation of the nickel-rich corner of the Ni-Cr-Ti, Ni-Cr-Al, and Ni-Ti-A1 systems. In the Ni-Ti and the Ni-A1 systems the hexagonal Ni,Ti phase, 7, and the cubic Ni3A1 phase, -y', respectively, exist in equilibrium with the nickel-rich solid solution. The interatomic distances in the basal plane of Ni,Ti and the octahedral planes of the matrix are almost equal, thus explaining the Wid-manstaetten type structure formed when Ni,Ti precipitates from solid solution. When Ni:,Al precipitates from solid solution, it appears usually in globular form, often dispersed along rows corresponding to definite crystallographic directions. The 7 and phases are also the only intermetallic compounds which occur in the nickel ternary alloys with up to 25 pct Cr and 10 pct Ti or Al. Taylor and Floyd found that Ni,Ti takes practically no nickel, chromium, or aluminum into solution. Nial, on the other hand, dissolves a considerable amount of chromium and titanium and some nickel. Up to three out of every five aluminum atoms could be replaced by titanium in Ni,Al. This substitution caused a slight increase (less than 1 pct) in the lattice parameter. With respect to the effect of variation in the titanium and aluminum contents on the high temperature strength of Nimonic 80 type alloys, Pfeil, Allen, and Conway" reported that an 80 pct Ni-20 pct Cr alloy containing 0.20 to 0.30 pct A1 had the highest creep resistance when the titanium content was kept between 1.65 and 2.75 pct. Experimental Procedure The materials used for this investigation were electrolytic nickel, electrolytic or low carbon chromium, sponge titanium and 2s aluminum. The alloys were melted in an indirect carbon arc furnace under

Jan 1, 1955

HeRbeRT Haas,—(communication to the Secretary*).—Fig. I plainly shows that the comparison of the steam-turbine and Diesel-engine plants was made on a basis of 6,000 kw. continuous operating load. The tabulation of costs for an 8,000-kw. load is merely done to show the relation of increased output on the unit power costs. Both plants would sacrifice their reserve capacity, which is to insure continuous operation, if operated to generate 8,000 kw. continuously; unless Mr. Hawkins advocates the operation of one of the turbines at 33.33 per cent. overload, retaining the other as a standby, which, besides overtaxing the turbine, results in a great loss of efficiency. It would be well for Mr. Hawkins to qualify certain of his statements. Thus, under the caption "Diesel Engines, Selection of Units," he says that '(two of the largest Diesel-engine builders take the position that, in the present state of the art, they would not attempt to put out units over 1,000 kw.;" he should qualify it by saying that "two of the largest American Diesel-engine builders take the position that, in the present state of the art in the United States, they would not attempt to put out units over 1,000 kw." The reason that American manufacturers restrict themselves at present to units of that size is to be found not so much in a lack of experience in building large units as in a lack of a sufficient demand for them in the United States to justify the heavy capital outlay connected with the development of such engines. There are relatively few localities in the United States where fuel prices are as high as they are in the South-, west, and regions of high fuel prices are sparsely settled and have a very limited demand for power. Where low fuel prices obtain, steam turbines are active competitors of Diesel engines for large power plants, particularly when the station load factor is low. As most of the American manufacturers of Diesel engines work under license agreements with European manufacturers, which limit their market to the United States and its possessions and Canada, a further limitation is imposed upon them, leaving to European firms practically the entire world as a market. The greater number of power plants range in size from 300 to 1,000 hp.; the average size of the central station, on a basis of all central stations in the United States, not greatly exceeding 500 kw.; in these sizes it is hard for steam engines to compete with Diesel engines, unless fuol oil prices are excessively high, and coal prices very low, or the exhaust steam is used for heating purposes.

Jan 1, 1917

By K. L. Komarek, P. F. J. Landler

Synthetic polycrystals of wustite were reduced ilz H2-H2O mixtures over limited roncentration ranges wiltun the wustite. field and the weight changes were continuously followed with a McBain quartz spiral balance. The reduction was. found to be controlled by a combined surface plus solid-state diffusion reaction. The solid-state diffusion had an activation energy of 38 kcal. Self--diflusioities of iron decreased with itzcreasing vacancy concentration. The activation energy of. the surface reaction runs different tor- different samples. The surface reaction-rate constan increased with increasirzg vacancy concentration. THE reduction of the oxides of iron has been studied for many years. Edstroem' has summarized the early work and has provided much information on the reduction of magnetite and hematite by hydrogen and carbon monoxide. More recent summaries are those by smeltzer2 and Themelis and Gauvin.3 Most investigators have reported that the iron metal which forms the outer layer during gaseous reduction is rather porous. According to Kohl and Engel14 the formation of such a porous iron layer depends on the properties of the underlying wiistite layer, on the reaction of the gas with the wustite surface, and on the transport of matter through the wustite layer. McKewan, Quets, Wadsworth, and Lewis, and Knacke 10 have found that, if a porous iron layer is formed, a surface reaction between gas and wustite at the bottom of the pores controls the rate of reaction. Seth and ROSS 11 and Warner 12 have pointed out that the influence of the gaseous pore diffusion through the porous iron layer cannot be neglected. It has further been shown that the wiistite layer formed during reduction is dense and that transport of matter across the layer occurs only by solid-state diffusion of iron ions.13,14 The solid-state diffusion rates observed by Edstroem and Bitsianis 14 and the surface reaction rates observed by Quets eta1.' show that an interaction of the two steps in controlling the reaction rate has to be considered. In this investigation the reduction of wustite was studied with respect to the interaction of the two steps, isolated from any other effects, by reducing wustite within the wustite field from higher to lower oxygen concentrations with H2-H2O gas mixtures. A similar study with CO-CO2 mixtures has been performed by Levin and wagner.15 Fused synthetic wustite polycrystals were reduced in steps of 0.4 wt pct from 24.4 to 23.2 wt pct 0 and over a temperature range from 700" to 1050°C. A few tests were also conducted with reduction steps from 24.4 to 23.6 wt pct 0 and 24.5 to 23.2 wtpct0. The Fe-O phase diagram is shown in Fig. 1 where the composition of the gas phase in equilibrium with the condensed phases is plotted as pct H2 vs the temperature. A careful study of the literature led to the conclusion that the fully drawn equicomposition curves (in wt pct O) in the wustite field used by Edstroem 1,16 and other authors needed some correction. Based on results by Darken and Gurry17 (shown as open circles) and on some of our own data, four corrected curves for 23.2, 23.6, 24.0, and 24.4 wt pct O were calculated (drawn as dashed lines in Fig. 1) which should replace the fully drawn equicomposition curves. MATERIALS AND APPARATUS Materials and Specimen Preparation. Wustite was prepared from iron sulfate (Fisher Scientific Co., New York) which had a purity of over 99.92 pct, with small amounts of manganese, copper, and zinc adding up to 0.03 pct. From the aqueous solution iron oxalate was precipitated and decomposed to magnetite according to Economos. 18 The magnetite powder was pressed into cylinders and sintered in vacuum at 900°C for several hours. The sintered compacts were placed in a platinum crucible of 2.5 cm diam which was fitted into a high-purity alumina crucible and then inserted into the center of the graphite heating element of an electric resistance furnace.lg The furnace was evacuated to below 1 p Hg and the magnetite sample was slowly heated. The evolution of gases during heating deter-

Jan 1, 1967

By J. N. Breston, R. V. Hughes

Conclusions drawn by previous research workers with reSPect to the relation between Pressure gradients and/or velocity and oil recovery obtained by laboratory water flood tests have been in disagreement probably due to variable procedures and unnatural conditions and materials. The Bradford Laboratory of the Pennsylvania Grade Crude Oil Association as part of its secondary recovery research program has conducted nineteen water floods on two long cores of widely differing characteristics in an attempt to clarify this relationship and make it an aid in predicting flooding pressures in the field. Unlike previous research procedures the present experiments were conducted with the aim of duplicating field conditions as closely as possible by using long unextracted consolidated cores, a live crude, and natural brines for both flooding and, connate water content. Also, the pressure gradients and flooding velocities were representative of field conditions where similar sands were being flooded. Eleven floods on one core and eight floods on the other core showed increased recoveries and lower residual oil saturation with increased flood pressure gradients and flood velocities. A marked decrease in recovery was obtained from both cores at very low flood velocities. This pressure versus recovery relationship is shown to hold up to the point of water breakthrough and also up to the 100 and 1 produced water to oil ratio point. INTRODUCTION The possibility of water flooding oil sands was suggested by Carl1 of the Pennsylvania Geological Survey in 1880. It is not known when the practice was tried intentionally for the first time, but its beneficial effects were noted in the annual production rate of the Bradford field as early as 1907. The practice was illegal in Pennsylvania until 1921. Early water floods in the Bradford field usually consisted of shooting or splitting the casing secretly to permit subsurface waters to enter the producing sands under hydrostatic head. As it was noted that the benefits of water flooding seemed to be proportional to the quantity of water dumped into the well many also began to utilize surface sources after the practice became legal. It was probably during the middle 20's before many producers realized that the pressurehead of the water upon the producing sand determined the rate and quantity of water that would enter the sand. Hence, rate and quantity of production appeared to be a direct function of input pressures. By 1927 a few producers had ventured the installation of pressure pumps in order to increase water-input rates and production through the combination of hydrostatic and hydraulic pressures. The adoption of pressure flooding and the "five-spot" drilling pattern in the Bradford field were essentially simultaneous. Water-input pressures in 1930 seldom exceeded 300 p.s.i. at the well head or 1100 p.s.i. at the sand face. Since that time, water-flood producers in the Bradford-Allegany fields have gone to higher and higher pressure until today 600 p.s.i. at the well heads is called a low pressure flood. Many high pressure floods now operate at 1300-1400 p.s.i. at the well head. The limiting and advisable pressure at the sand face has been pronounced as that pressure just under what is required to lift the overburden or to cause formation parting: According to this rule any water flood operation utilizing well-head pressures nearly equal in pounds per sq. in. to 1.1 times the average depth in feet to the top of the producing sand would be considered as a high-pressure flood. Despite the higher pressure trends in the Bradford-Allegany field operations and the results of early laboratory water flooding research, the desirability and benefits of high input pressures are still questioned by many operators, particularly in midwestern water flood operations. The present paper recounts a series of 19 laboratory water floods using two long, consolidated cores of widely differing characteristics saturated with live crude and flooded with oil field brines in an effort to simulate field conditions under • various pressure gradients and flooding velocities. For both cores, higher recoveries and lower residual oil saturations were obtained at higher pressure gradients and flood velocities. This relationship is shown to hold up to the water breakthrough point and also up to the 100 to 1 produced water to oil ratio point.

Jan 1, 1949

By R. V. Hughes, J. N. Breston

Conclusions drawn by previous research workers with reSPect to the relation between Pressure gradients and/or velocity and oil recovery obtained by laboratory water flood tests have been in disagreement probably due to variable procedures and unnatural conditions and materials. The Bradford Laboratory of the Pennsylvania Grade Crude Oil Association as part of its secondary recovery research program has conducted nineteen water floods on two long cores of widely differing characteristics in an attempt to clarify this relationship and make it an aid in predicting flooding pressures in the field. Unlike previous research procedures the present experiments were conducted with the aim of duplicating field conditions as closely as possible by using long unextracted consolidated cores, a live crude, and natural brines for both flooding and, connate water content. Also, the pressure gradients and flooding velocities were representative of field conditions where similar sands were being flooded. Eleven floods on one core and eight floods on the other core showed increased recoveries and lower residual oil saturation with increased flood pressure gradients and flood velocities. A marked decrease in recovery was obtained from both cores at very low flood velocities. This pressure versus recovery relationship is shown to hold up to the point of water breakthrough and also up to the 100 and 1 produced water to oil ratio point. INTRODUCTION The possibility of water flooding oil sands was suggested by Carl1 of the Pennsylvania Geological Survey in 1880. It is not known when the practice was tried intentionally for the first time, but its beneficial effects were noted in the annual production rate of the Bradford field as early as 1907. The practice was illegal in Pennsylvania until 1921. Early water floods in the Bradford field usually consisted of shooting or splitting the casing secretly to permit subsurface waters to enter the producing sands under hydrostatic head. As it was noted that the benefits of water flooding seemed to be proportional to the quantity of water dumped into the well many also began to utilize surface sources after the practice became legal. It was probably during the middle 20's before many producers realized that the pressurehead of the water upon the producing sand determined the rate and quantity of water that would enter the sand. Hence, rate and quantity of production appeared to be a direct function of input pressures. By 1927 a few producers had ventured the installation of pressure pumps in order to increase water-input rates and production through the combination of hydrostatic and hydraulic pressures. The adoption of pressure flooding and the "five-spot" drilling pattern in the Bradford field were essentially simultaneous. Water-input pressures in 1930 seldom exceeded 300 p.s.i. at the well head or 1100 p.s.i. at the sand face. Since that time, water-flood producers in the Bradford-Allegany fields have gone to higher and higher pressure until today 600 p.s.i. at the well heads is called a low pressure flood. Many high pressure floods now operate at 1300-1400 p.s.i. at the well head. The limiting and advisable pressure at the sand face has been pronounced as that pressure just under what is required to lift the overburden or to cause formation parting: According to this rule any water flood operation utilizing well-head pressures nearly equal in pounds per sq. in. to 1.1 times the average depth in feet to the top of the producing sand would be considered as a high-pressure flood. Despite the higher pressure trends in the Bradford-Allegany field operations and the results of early laboratory water flooding research, the desirability and benefits of high input pressures are still questioned by many operators, particularly in midwestern water flood operations. The present paper recounts a series of 19 laboratory water floods using two long, consolidated cores of widely differing characteristics saturated with live crude and flooded with oil field brines in an effort to simulate field conditions under • various pressure gradients and flooding velocities. For both cores, higher recoveries and lower residual oil saturations were obtained at higher pressure gradients and flood velocities. This relationship is shown to hold up to the water breakthrough point and also up to the 100 to 1 produced water to oil ratio point.

Jan 1, 1949

By R. W. Armstrong, P. C. Jindal

The hardness dependence on grain size for polycrys-talline cartridge brass and a leaded brass has been measured by Brine11 and Rockwell B testing. In each case, the hardness, H, depends on the average grain diameter, 1, according to: H =Ho + kHl-1/2 where Ho and kH are experimental constants. Diamond pyramid hardness values have also been measured as a function of the indentation size and grain size to give additional information on the nature of the hardness test and the dependence of hardness on micro-structure. The hardness of polycrystalline brass depends on its grain size. Bassett and Davis' demonstrated this as early as 1919 by making Brinell hardness measurements on cartridge brass. Since then, the hardness of this type of material has been measured as a function of grain size by making Rockwell,2'3 Vickers,4 and Brinell5 tests. he hardness dependence on grain size has also been measured for other materials. Angus and summers6 investigated the grain size dependence of the Brinell hardness of polycrystalline copper and a Cu-4.5 pct Sn bronze. In other studies, nickel,? Armco iron,Big an Fe-0.07 pct C alloy,I0 and an 0.39 pct C-12.45 pct Cr stainless steel" have been investigated. In some of the preceding cases, the hardness results have been analyzed to show that the hardness varies with the average grain diameter, 1, according to an l-l\4, l-1/4 or I-2 dependence,11-13 The studies of the influence of grain size on hardness have not been based on any theoretical model. This may be because the hardness of a material is itself a complicated property. However, attempts have been made to correlate, experimentally and theoretically, the hardness of a material with its unidirectional stress-strain behavior.14-l6 On this basis, Hall" proposed that the polycrystal hardness dependence on grain size might follow directly from the Hall-Petch18,19 relation for the grain size dependence of the yield stress. Thus, the hardness-grain size relation was given as: H = Ho + kHl-1/2 [1] where Ho and kH were taken as experimental constants. The relation was applied to the measurements on brass,' copper,6 bronze,= and Armco iron.' More recently, this relation was shown by Armstrong and jindal20 to adequately describe the measurements on cartridge brass made by Bassett and Davis' and Babyak and Rhines.5 In this case, the relationship was taken a step further by independently relating the values of Ho and kH to the values of oyand ky, previously reported by Armstrong, Codd, Douthwaite, and petch21 from measurements of the yield stress dependence on grain size for this type of material. In the present investigation, new Brinell and Rockwell B hardness measurements have been made as a function of grain size for a cartridge brass and a leaded brass. In addition, diamond pyramid hardness values were measured as a function of the indentation size. All these results are applied to a further analysis of the hardness dependence on grain size. MATERIALS AND EXPERIMENTAL METHODS Cartridge brass and a leaded brass were selected for this investigation for two main reasons: it was anticipated 1) that these materials could be cold-worked and recrystallized to a wide range in grain size and 2) that the results to be obtained on these typical industrial materials could be usefully compared with previous investigations. The chemical analyses of the actual materials which were employed are given in Table I. The as-received 1/2- and 3/4-in.-thick plates were given various reductions in thickness by cold rolling. The rolled material was heat-treated at various temperatures between 330" and 850°C for differing time periods from 5 min to 9 hr to achieve a variation in the average grain diameter between 0.0339 and 0.000543 cm.22 During heat treatment, the brass was protected from zinc loss by packing it in chips or foils of the same composition material. Reasonably equi-axed grain structures were obtained in each case. The metallurgical grain sizes of the specimens were determined from measurements of the average linear intercept on a random line. Annealing twin interfaces were not counted along with grain boundaries. The

Jan 1, 1970

By N. J. Grant, A. W. Mullendore

Three aluminum alloys of 0.94, 1.92, and 5.10 pct Mg, prepared from very high purity metals, were tested at 500°, 700°, and 900°F in creep rupture. The degree of strengthening through solid-solu-tion alloying and the effects on the deformation characteristics and fracture were examined. The ductility of the alloys as a function of stress and temperature was closely followed. STUDIES of the creep process in pure metals in recent years have done much to expand the understanding of the fundamental deformation and recovery processes that contribute to overall creep behavior. In order that this knowledge may be applied to commercial alloys, it is necessary to know the principles governing the effect of alloying on the mechanisms of creep. A limited amount of work has been performed in this field, but few investigators have attempted to follow the changes in particular creep mechanisms with alloying. Recently, studies of the effects of solid-solution alloying on the plastic properties of aluminum have been conducted by Dorn, Pietrokowsky, and Tietz,1 Sherby, Anderson, and Dorn,2 and Sherby and Dorn.3 This paper presents the results of an investigation of the effect of solid-solution alloying of high purity aluminum with magnesium on the creep-rupture properties, and correlates these observations with changes in the creep mechanisms. This work is thus an extension of the creep-rupture observations of Servi and Grant4,5 and the deformation studies of Chang and Grant.6,7 Experimental Procedure Three alloys of aluminum containing approximately 1, 2, and 5 pct Mg were tested. These alloying additions are all within the solid-solubility limit at the testing temperatures.' The analysis of the materials is presented in Table I. The tests fall into two categories: l—creep-rup-ture tests at 500°, 700°, and 900°F, and 2—structure study tests performed primarily at 700°F. Speci-mens of 0.160 in. diameter with milled flats for metallographic observations" ' were utilized for the structure studies. All specimens were annealed in one step to give the desired grain size for the tests. Table II presents the annealing data and final grain sizes. The specimens were polished electrolytically before testing with Jacquet solution (2/3 acetic anhydride, 1/3 perchloric acid) at 25" to 30°C, and 15 to 20 v. Creep-rupture testing was performed under constant load with the apparatus previously described." Results and Discussion Creep-Rupture Properties: The log-log plots of creep-rupture data are presented in Figs. 1 and 2. For these very pure single-phase alloys, the minimum creep rate and the rupture life both exhibit straight-line dependence on stress in this method of plotting as they have for commercial alloys0,10 and for pure aluminum." Curve breaks, based on the use of straight-line segments, at 500°F have been found by metallographic study to correspond to a transition from low to high temperature behavior and so represent zones of equicohesion. Specimens on the high creep-rate side of the break showed normal granular deformation processes whereas those on the low creep-rate side showed rapidly increasing grain-boundary sliding and migration with extensive evidence of intercrystalline cracking at 500°F. Two micrographs of the 0.94 pct Mg alloy, Fig. 3, show the increased participation of the grain boundary in the deformation process at 500°F with decreasing stress. In Fig. 3a is shown the structure of a specimen which exhibits little deformation along the grain boundaries and failed transgranularly; in Fig. 3b is shown the increased deformation along the grain boundaries at a lower stress for a specimen which showed appreciable intercrystalline cracking. The severity of intercrystalline cracking increased with increasing magnesium content at 500°F. Intercrystalline cracking disappeared in most of the specimens at 700°F and persisted only in the 5 pct Mg alloy at high creep rates. At 900°F all of the specimens deformed with extensive grain-boundary participation, including extensive grain-boundary migration. None of the alloys at 900°F showed intercrystalline cracking.

Jan 1, 1955