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By Emil Gathmann

(San Francisco Meeting, September, 1915) THROUGH wide experience at numerous mills in the United States I have found that there is a decided difference of opinion among the producers of steel as to what constitutes commercially sound steel. Some metallurgists insist upon having, for certain grades of steel, a so-called "open steel," -i.e., one which contains numerous blowholes of varying sizes, and consequently but little volume of true pipe, although a central intermittent shrinkage cavity often extends well down into the ingot: Such blowholes and pipe are expected to weld up during rolling or forging, because their surfaces are not oxidized. Even if this be admitted, included slag particles and a high degree of segregation are bound to be present in the product of such ingots. Blowholes are the result of an oxidized heat, and all heats, unless made or finished in the electric furnace, are oxidized more or less. Subsequent deoxidation, or rather degasification, either in the ladle or in the mold, or in both, is necessary to reduce or prevent blowholes. As is well known, a greater yield of billets or sheets is secured from the ingot by allowing the formation of blowholes, but this is undoubtedly obtained at the expense of the quality of the product. Decided segregation of carbon, phosphorus, and sulphur, as well as small included slag particles, undoubtedly exists throughout the greater portion of all so-called open steel, and cannot be removed by cropping. The first requisite for sound, homogeneous steel ingots and blooms is therefore, in my opinion, so to treat the steel in the furnace, ladle, and mold that "piping" steel is produced. The line of demarcation between harmful and so-called "harmless" blowholes is practically impossible to define. Is it not, therefore, the better and safer practice to use means for the elimination of blowholes and correspondingly reduce the segregation and allow the formation of a well-defined shrinkage cavity or pipe .at the upper end of the ingot? With the relatively cheap deoxidizers available at the present time, e.g., ferro-silicon, aluminum and titanium,

Jan 8, 1915

By Ernst A. Hauser

A few years ago an Indian native of British Columbia drew the attention of white men,' to a deposit of a claylike material on King Island, at the mouth of Dean River just opposite Hunter Island in the Pacific Ocean (Fig 1 ) . The native claimed that this natural product, which is found not in solid form but either as a paste or as a thick, viscous liquid, exhibited exceptional healing properties not only for various types of skin irritation but also for internal ailments. He pointed out that the natives had been using this material very successfully for generations. Since then, systematic surveys have revealed that the deposit, covered by a humus layer of varying thickness, is far more extensive than had originally been assumed. The product as mined today is of puttylike consistency and of greenish color. If exposed to air it dries rapidly, forming a slightly gray, rather brittle product, which does not permit redispersion to its original consistency. When the natural product is rubbed on the skin, however, the presence of coarse, sandy material is revealed.

Jan 1, 1952

By E. J. Nielsen, P. R. Strutt

A study has been made of the progressive changes in the distribution of etch-pit structures occurring during high-temperature creep in copper + 7 wt pct Al single crystals oriented with a [113] tensile axis. The two equally stressed glide systems with the highest Schmid factor would be expected to form subboundaries of the type predicted by Kear.2 The alignments of etch-pits on sections parallel to different (111} planes consistent with these types of boundaries were not observed. However, they were consistent with planar subboundaries (on a macroscopic scale). From an analysis of Amelinckx1 it may be shown that stable cross-grid dislocation boundaries may form in the primary slip planes. These boundaries form when dislocations with a Burgers vector not in the slip plane move into the plane by combination of climb and glide. THE geometry of subboundaries formed by the interaction of dislocations of two glide systems has been analyzed by Amelinckx,1 and the particular types produced by deforming fee crystals are predicted by ear.' In this paper types of boundaries which may be formed when climb as well as glide occur are discussed as this is relevant in high-temperature creep. It is assumed in the present investigation that the etch-pits observed in Cu + 7 wt pct A1 on surfaces parallel to {111} planes delineate the sites of dislocations. Although there is no direct evidence for this previous work on a-Cu/Al single crystals by Mitchell, Chevrier, Hockey, and Mon-aghan,3 would show this assumption to be reasonable. The alignments of etch-pits which form during creep are studied on sections parallel to each {111) plane. It is then deduced that these alignments are consistent with a specific type of planar subboundary. The Cu + 7 wt pct A1 single crystals had a [113] tensile axis and Fig. 1(a) shows schematically the relation of the slip planes and slip directions (as represented by tetrahedron ABCD) with reference to the tensile axis. The two equally stressed glide systems with the maximum Schmid factor namely ß-AD and (a-BD, from the analysis of Kear,2 would be expected to form the boundaries shown in Fig. l(a) and (b), also Fig. 5(a) and (b). EXPERIMENTAL PROCEDURE The a-Cu/Al single crystals were grown and annealed in a "gettered" argon atmosphere. Chemical analysis showed the aluminum content to be uniform in each crystal and the difference between crystals was maintained to an accuracy of ± 0.25 wt pct. The initial dislocation density and mean subgrain diameter after annealing was -106 cm-2 and 250 µ, respectively. Surfaces parallel to (111) planes were produced by specially developed electrolytic machining processes. The {111} faces were next electropolished for 5 min in a solution consisting of 25 g chromium trioxide, 113 ml glacial acetic acid and 40 ml water; the applied potential was 8 v. Dislocation etch-pits were revealed using l an etchant described by 1 ml bromine, 45 ml HCl, and - 250 ml water. RESULTS In crystals strained into secondary creep at higher stresses (443 and 750 g - mm-2 at 650° C aligned rows of etch-pits parallel to slip plane traces were evident in sections parallel to the (1111, (ill), and (111) planes, see Fig. 3. As well as the longitudinal alignments in Fig. 3, well formed randomly oriented arrays indicative of an equiaxed subgrain structure are evident. At the lower stresses (100 to 230 g . mm-2) only an equiaxed structure formed during creep. The sections in Fig. 3 are from a crystal crept for 70 hr at 650°C with a CRSS of 443 g.mm-2. Two identically oriented crystals were also deformed at the same temperature and stress for 5 min and 4 hr. In the crystal crept for 5 min, the etch-pits were randomly distributed with no tendency for directional alignment, see Fig. 2(a). As shown in Fig. 2(b) aligned arrays were evident after 4 hr creep but they were not nearly so well defined as in Fig. 3. The alignments (parallel to the arrows) in Fig. 3 are consistent with the existence of boundaries in the two main slip planes a and ß. The way in which this is deduced is seen by reference to Fig. l(c), where the existence of boundaries in the a and ß planes is verified by sectioning parallel to a,ß, and d. The (111) and ß(111) planes intersect the d(111) plane along BC [101 ] and AT [011] and alignments parallel to [101] and [011] are clearly evident in Fig. 3(c) in a section parallel to the d(111) plane. Similarly the a, and ß planes in Fig. l(a) intersect each other along DC [110] and hence there will be an alignment parallel to [110 ] in sections parallel to the a-plane and the ß-plane; this is evident in Fig. 3(a) and Fig. 3(b). It is interesting to note that alignments of etch-pits consistent with the boundaries predicted by Kear2 were not observed; see Figs. l(a) and l(b). The geometry of boundaries in {111} planes as shown in Fig. l(c) is discussed later. In Fig. 4(a) the individual etch-pits are resolved and the alignments are exactly parallel to the slip trace direction [101]. However, in some areas alignments deviate away from the slip trace direction by as much as 10 to 15 deg, this is evident in Fig. 4(b), and in Fig.

Jan 1, 1969

By W. W. Schmittroth, A. Y. Bethune

THE commercial analysis of Special High-Grade zinc usually involves the determination of lead, iron, copper and cadmium as impurities in the base metal. Over the past 20 years, as the result of metallurgical improvements in the art of producing Special High-Grade zinc metal there has taken place a gradual exclusion of almost all extraneous elements, and the few that do remain in the final product have been virtually reduced to the vanishing point. Thousands of tons of zinc .are now commercially produced annually and made available to the trade, in which impurities are present only in the order of 0.0010 per cent or less and the sum total of all impurities does not exceed 0.0025 per cent. To such zinc the term "superpurity" might well be applied without undue exaggeration. The techniques used for production control and final analysis of Special High-Grade zinc by means of emission spectra in the laboratories of the electrolytic zinc plant of the Sullivan Mining Co. are based on the premise that self-electrodes are to be preferred over all other forms for the examination of the zinc in question. Furthermore, after a survey of the literature and considerable experimental work,1 it was decided that the spectrographic method of internal control, the principle of which was first announced by Gerlach,2 using a modification of the high-voltage alternating-current arc source introduced by Duffendack and Thompson,3 with the calibration of each photographic plate as recommended by Wolfe,4 would yield the most accurate and reproducible results. Self-electrodes were chosen in order to make use of one of the unique advantages inherent in spectrographic analysis; namely, the rapid and almost effortless detection of elements other than those being quantified by the analyst; or conversely, the proof that the zinc is free from such impurities if no spectral line of the suspected element appears. This fact was verified for certain elements, and will be discussed later. Carbon electrodes impregnated or packed with zinc salts chemically prepared from the zinc to be assayed were avoided for a number of reasons. First, the chemical manipulation was another time-consuming step, which increased the chances for contamination. Second, none of the common zinc salts, such as the chloride, nitrate or sulphate, yielded reproducible results under our conditions, nor did the spectral line of the impurity appear as readily in the low concentrations as when using zinc metal. Third, no commercial carbon, except the very expensive, was pure enough to use with this grade of zinc and the continued time, effort and expense incurred in the purification of carbon was not desirable. The use of Special High-Grade zinc self-electrodes introduces certain complications with regard to obtaining satisfactory excitation conditions, because it seems necessary to raise the temperature

Jan 1, 1946

By G. R. Speich, D. J. Mack

The transformation of was studied by isothermal methods. At all temperatures, the ß transforms quickly to fine grained ß" which develops silver-rich striations. At higher temperatures the striations disappear, the final structure being Widmanstatten a in ß'. At lower temperatures, the striated ß" is consumed by pearlite nodules of a + ß' which in turn form the Widmanstatten a in ß'. The transformation is unlike any previously reported for a eutectoid. AS part of a general program of study on the eutectoid reaction, the Ag-Cd eutectoid seemed particularly attractive because the ß phase which undergoes the reaction is another of the typical "electron compounds," AgCd, having the disordered body-centered cubic structure. This work deals with the eutectoid which occurs at 50.5 wt pct Ag, and not with the eutectoid which has been reported at 42.9 pct Ag.' There has been no work reported specifically on the Ag-Cd eutectoid which was studied. The only information available on this eutectoid is that work done in the determination of the phase diagram. For the most part, the terminal portions of the diagram, Fig. 1, are well established; however, the region from 40 to 60 pct Cd is still somewhat in doubt. The X-ray evidence'..' in this region is in conflict with the results of thermal analysis. X-ray analysis3 does not show a polymorphic transformation at about 240°C as indicated by thermal analysis.1,5 Even the X-ray evidence, within itself, is confusing in this region of the diagram. One investigator2 reports the ß phase as hexagonal close-packed and has found three phases in the one-phase ß field. Other X-ray investigators"' ' report the ß phase as body-centered cubic. The authors believe that much of the confusion resulted from incomplete homogenization of the alloys. It was found that it takes almost a week to produce a completely homogeneous two-phase structure at 370°C. Another possible source of error is the volatilization of cadmium from the surface and cracks of the specimen during annealing with the possible formation of a cadmium-poor phase. The only metallographic data available on this eutectoid alloy are those of Durrant1 and Fraenkel and Wolff.5 his information is very limited. The phase diagram chosen as most nearly correct is that in the Metals Handbook," which is almost identical with the phase diagram suggested by Durrant.1 Materials and Procedure The alloy was prepared from high purity silver (999.5 plus fine) and high purity cadmium (0.02 Pb, 0.005 Cu, trace Fe). The metals were melted in carbon under a nitrogen atmosphere. Some cadmium was lost by volatilization but by remelting several times and adding cadmium a 200 g ingot of approximately eutectoid composition was obtained. Because the CdO fumes are quite toxic, the exit gas from the furnace was led through a water trap to condense the CdO. The ingot was homogenized at 650°C for 24 hr, no attempt was made to prevent decadmiumization. This resulted in a narrow decadmiumized rim on the ingot which was removed. Filings for analysis were obtained from cross sections of the ingot. Silver was determined by the Volhard thiocyanate method,? cadmium by difference. The ingot analyzed 50.8 pct Ag at the top of the ingot and 50.7 pct at the middle and at the bottom of the ingot. This alloy was only slightly hypo-eutectoid compared to the accepted value of 50.5 pct Ag and was used for the isothermal studies. It was felt that further attempts to adjust the composition might be futile because of the volatility of the cadmium. The ingot was sectioned to specimens approximately 3/4 x 3/4 x 1/8 in. These specimens were "austeni-tized" for 3 hr in air at 650°C to yield homogeneous ß and then quenched into a salt bath held at constant subeutectoid temperatures where the transformation

Jan 1, 1954

By James C. M. Li

The Petch relation between the flow stress and the gain size is derived from a consideration of gain boundary sources of dislocations without the need of dislocation Pile-ups. Three mechanisms for inierpreting the yield stress: the gain boundary strength, the unpinning of Frank-Read source near a grain boundary, and the generation of dislocations from the grain boundary are compared and the condition of their equivalence is shown. The effect of the average angle of misfit of pain boundaries is found to be sma11 and so is that of the average angle of misfit of subboundaries having impurities. The effect of impurities on the ledge density in the grain boundary is treated thermodynamically and a relatwn is proposed for the variation of Petch slope with impurity activity. The effect of temperature on the Petch slope is interpreted as due to the change of ledge structure in the grain boundary. It is indicated that the effect of annealing temperature may be more important than that of the test temperature and therefore should be studied. The effect of plastic strain on the Petch analysis is deduced from a work-hardening equation in which the generation of dislocations has first-order kinetics and the annihilation of dislocations has second-order kinetics. It is concluded that the Petch slope will decrease with plustic strain if the rate of annihilation of dislocations is sufficiently large. Critical experiments which may shed light on the mechanism for the Petch relation are suggested. THE relation between the yield or flow stress, 0, and the grain size, l, was first proposed by all' and later studied more extensively by Petch and co-workers, who also proposed a similar relation for the fracture stress and deduced from these a grain-size effect of the ductile-brittle transition temperature. The microscopic mechanism used by all' and petch2 involves a pile-up of dislocations of like sign generated from a Frank-Read source. The yielding or flow takes place when the pile-up exerts sufficient stress at the grain boundary so that the plastic deformation can propagate from one grain to another. If the average strength of the grain boundary is ai and the average length of the pileup is lp, the Petch slope, k, is given by" where p is the shear modulus, b the Burgers vector, and v the Poisson ratio. This slope will be independent of the grain size if l/lp is a constant. This is possible, since, if the Frank-Reed source is situated near the grain boundary, lp = 1, and if it is situated in the middle of the grain, Ip = 1/2. cottrell,12 also using the pile-up mechanism, proposed that the stress concentration at the grain boundary will initiate Frank-Read sources near the grain boundary and in this manner a Lüders band can propagate from one grain to another. Assuming that the average distance between the Frank-Read sources and the grain boundary is 1, and the unpinning stress of the Frank-Read sources is op, Cottrell obtained the following Petch slope: This slope will be independent of the grain size if ls is independent of the same, which is not as obvious as the condition, Ip = I for Eq. [2]. In addition to this assumption, the direct relation between the Petch slope k and the unpinning stress, up, was recently questioned by Johnsonon grounds that it is inconsistent with the following observations: the independence of k with temperature and strain rate, and the small k in columbium, which, like iron, has a sharp yield point. As pointed out by ohnson," the most important objection both to the Hall-Petch mechanism, in which the strength of the grain boundary plays the role in yielding, and to the Cottrell mechanism, in which the unpinning of Frank-Read sources plays the role in yielding, is the lack of direct observation of the pile-ups. The dislocation structure in deformed iron has been examined recently in the electron microsope.'-' Dislocations appear to be generated from grain boundaries or other interfaces; they form clusters and tangles within the grain at very early stages of deformation, even in the Lüders band, if the deformation is slow or at normal and elevated temperatures. Although it is still too early to interpret bulk properties from thin-film observations, it does seem worthwhile to look for a mechanism for the Petch relation which does not require dislocation pileup. SUBBOUNDARY SOURCES In order to show that a consideration of grain boundary sources can lead to the same Petch relation as does the consideration of the strength of the grain boundary, we shall first discuss the case of a simple tilt boundary whose elastic properties have been studied in detail.17 The strength of a partially

Jan 1, 1963

By J. H. Jackson, P. D. Frost, C. H. Lorig, L. W. Eastwood, A. C. Loonam

It is well known that for equal weights of material, thin sections of the lighter structural alloys are more resistant to buckling under a compressive stress than thin sections of more dense material. Therefore, structural parts having the same resistance to buckling stresses are generally lightest when they are made of magnesium alloys. Consequently, there is considerable interest in the development of strong alloys having densities equal to or lower than that of magnesium and strength-weight ratios equivalent to those of the strongest aluminum alloys. The development of commercial magnesium-base alloys has been very successful, and their importance among materials in the structural field has been amply demonstrated. However, an even wider structural application of magnesium alloys might be effected if improvements could be made in the cold rollability and cold-forming characteristics. Such improvements, along with production of less directionality in properties. could be effected if the hexagonal close-packed lattice of present alloys could be replaced with a cubic lattice. In 1942, a project, having as its objective the improvement of some of the characteristics of commercial magnesium-base alloys, was initiated at Battelle Memorial Institute under the sponsorship of the Mathieson Chemical Corporation. At that time, one of the authors,* then Chief Metallurgist for the Mathieson Chemical Corporation, postulated that the addition of lithium to magnesium in sufficient quantities to change the crystal structure of the resultant alloy from a hexagonal to a body-centered cubic lattice should produce a magnesium-rich alloy which would have the desired improvements in cold-working characteristics with less directionality in properties. To test this view, a series of alloys was made and was found to have many of the attributes that were predicted. The view that magnesium-lithium alloys were of structural interest was also held by others. In 1943 and 1945, Dean and Andersonl,² obtained patents on magnesium-base alloys containing from about 1 to 10 pct lithium, from about 2 to about 10 pct manganese, and the balance substantially all magnesium; and on magnesium-base alloys containing from about 1 pct to about 10 pct lithium, from about 2 to about 10 pct manganese, from about 0.5 to 2 pct silver, and the balance substantially all magnesium. They noted that an alloy containing 83 pct magnesium, 10 pct manganese, 5 pct lithium, and 2 pct silver could be cold rolled by any of the usual methods and that this alloy was considerably harder and stronger than most other magnesium-base alloys heretofore available. In 1945, Hume-Rothery, et al.,3 predicted that magnesium-lithium base alloys should be soft and ductile and that such compositions, to which was added a third element for the purpose of producing a precipitation-hardening type of alloy, should be ductile, strong, and lighter than magnesium itself. Hume-Rothery investigated the binary magnesium-lithium and ternary magnesium-lithium-silver equilibrium relations and criticized the existing equilibrium diagrams. The binary magnesium-lithium equilibrium diagram has also been investigated by Grube, Von Zeppelin, and Bumm, Henry and Cordiano, Sal'dau and Shamrai, Hof-mann,' and Shamrai.8 The work of most investigators agreed with that of Grube, whose constitution diagram is shown in Fig 1. From the standpoint of development of structural alloys, the room-temperature equilibrium relations are of great interest. An examination of Fig 1 reveals that, from 0 to 5.7 pct lithium, the existing phase is alpha, which is a solution of lithium in hexagonal magnesium. The boundary between the alpha, and alpha plus beta regions, occurs at a Mg/Li of 16.5, corresponding to 5.7 pct lithium by weight. Between 5.7 pct and 10.3 pct lithium, there exists a mixture of the alpha phase (lithium dissolved in hexagonal magnesium) and the beta phase (magnesium dissolved in body-centered-cubic lithium). The boundary of the alpha plus beta and beta regions occurs at a Mg/Li of 8.7, corresponding to a lithium composition of 10.3 pct. Much of the work described here was directed toward obtaining an alloy made up of a large proportion, or entirely, of the body-centered-cubic beta structure. In his early work, Loonam found that specimens of lithium-bearing alloys were very malleable. Ingots of alloys prepared at that time were extruded to 3/8-in. diam bars, and the mechanical properties and the effects of heat treatment were then determined. These data are given in Table 1. The outstanding ductility of the alloys, combined with their moderately high strength, evoked considerable interest.

Jan 1, 1950

By John C. Branner

Stratigraphic Position of the Deposits.—During the progress of the geological survey of Arkansas, in the northern part of that State, it was found that the interval between recognizable Lower Silurian rocks below and recognizable Lower Carboniferous rocks above contains no representatives, or but poor representatives, of the whole Upper Silurian and Devonian series. In some places one passes in the space of a foot from Lower Silurian rocks to the Lower Carboniferous—the Boone chert of the Arkansas survey, or the " Burlington " beds; at other places this interval is 3 or 4 feet thick, but it is generally concealed by the ready decay of the black shale—the Eureka shale—which fills it, so that for a long time it was passed over undetected. It was only after considerable work in the region lying north of the Boston mountains, and by the valuable palzeontologic work of Dr. Henry S. Williams, of Yale University, who kindly accompanied me on a trip through this part of the State, that the importance of this interval came to be recognized, and the thin beds occupying it to be critically studied. It then appeared that this interval was occupied, for the most part, either by a greenish or black shale or by a sandstone; and eventually the sandstone was found to have a maximum thickness of 40 feet on South Sylamore creek in 15 N. 11 W., Section 21. It was, therefore, called Sylamore sandstone. The shale of this interval is generally from 3 to 10 feet thick; it is a constant feature of the geology through Carroll county, and is well exposed in the streets and cuts in and about Eureka Springe, and was for this reason named the Eureka shale. Its maximum thickness is 50 feet in the northwestern part of Benton county. The relations to each other of the Sylamore sandstone and the Eureka shale I have never determined satisfactorily; for

Jan 1, 1897

By M. Muskat, M. O. Taylor

Theoretical calculations have been made on the performance to be expected of gas-drive reservoirs for various characteristics of the oil and gas and the producing rock. Such performante has been expressed graphically as curves for the reservoir pressure and gas-oil ratios of the production as functions of the cumulative oil recovery. The latter has been expressed in terms of percentage of pore space of the reservoir rock. Such curves automatically give values for the ultimate physical recovery, if the latter is interpreted as the recovery obtained when the reservoir pressure has declined to atmospheric, or to any other pressure chosen as defining the state of practical complete depletion. Calculations of these pressure and gas-oil ratio histories have been made for conditions in which the oil viscosity, the gas solubility and shrinkage, the size of an overlying gas cap, if present, the permeability-saturation characteristics of the rock, and the amount of connate water, have been individually varied, The results serve to show the extent to which the ultimate recoveries are sensitive to the important physical parameters characterizing the oil reservoir. As is to be expected, the ultimate recoveries are found to decrease with increasing oil viscosity. Because of the predominant effect of the oil shrinkage associated with the liberation of the gas in solution, the ultimate recovery will decrease with increasing gas solubility. Increasing gas-cap volumes lead to higher recoveries, although the contribution made by the gas-cap gas is small as compared with the oil expulsion by the equivalent amount of solution gas. As a whole, the oil recovery when expressed in percentage of the pore space is not very sensitive to the details of the permeability-saturation relationship. However, if the rocks possess an equilibrium free-gas saturation, the rise in gas-oil ratio will be retarded, and the 'ultimate recovery somewhat increased' The oil shrinkage associated with the liberation of the dissolved gas also leads to the result that as long as the connate water is immobile and the permeability ratio curve for the rock is a function only of the total liquid saturation, the stock-tank oil recovery will be less for a sand containing no connate water than for One with an Original water content as high as 3' per cent. The space voidage in the former case will be somewhat greater, but the effect of oil shrinkage will lead to smaller values for the equivalent stock-tank recovery. These calculations also give data showing how the productivity indexes for the producing wells will vary during the reservoir history. Because of decreasing Permeability to the oil and increasing oil viscosity, the productivity index will fall continuously as Production proceeds, and may finally reach values as low as 10 per cent of the initial productivity index. Introduction In a previous paper1 was developed the basic theory for the prediction of the production histories of gas-drive reservoirs. The data required for the application of this theory included the characteristics of the petroleum fluids, such as the viscosity of the Oil and gas phases, the solubility of the gas in the oil, and the oil shrinkage— all expressed as functions of the reservoir pressure—and the permeability-saturation characteristics of the producing rock, as

Jan 1, 1946

By M. Muskat, M. O. Taylor

Theoretical calculations have been made on the performance to be expected of gas-drive reservoirs for various characteristics of the oil and gas and the producing rock. Such performante has been expressed graphically as curves for the reservoir pressure and gas-oil ratios of the production as functions of the cumulative oil recovery. The latter has been expressed in terms of percentage of pore space of the reservoir rock. Such curves automatically give values for the ultimate physical recovery, if the latter is interpreted as the recovery obtained when the reservoir pressure has declined to atmospheric, or to any other pressure chosen as defining the state of practical complete depletion. Calculations of these pressure and gas-oil ratio histories have been made for conditions in which the oil viscosity, the gas solubility and shrinkage, the size of an overlying gas cap, if present, the permeability-saturation characteristics of the rock, and the amount of connate water, have been individually varied, The results serve to show the extent to which the ultimate recoveries are sensitive to the important physical parameters characterizing the oil reservoir. As is to be expected, the ultimate recoveries are found to decrease with increasing oil viscosity. Because of the predominant effect of the oil shrinkage associated with the liberation of the gas in solution, the ultimate recovery will decrease with increasing gas solubility. Increasing gas-cap volumes lead to higher recoveries, although the contribution made by the gas-cap gas is small as compared with the oil expulsion by the equivalent amount of solution gas. As a whole, the oil recovery when expressed in percentage of the pore space is not very sensitive to the details of the permeability-saturation relationship. However, if the rocks possess an equilibrium free-gas saturation, the rise in gas-oil ratio will be retarded, and the 'ultimate recovery somewhat increased' The oil shrinkage associated with the liberation of the dissolved gas also leads to the result that as long as the connate water is immobile and the permeability ratio curve for the rock is a function only of the total liquid saturation, the stock-tank oil recovery will be less for a sand containing no connate water than for One with an Original water content as high as 3' per cent. The space voidage in the former case will be somewhat greater, but the effect of oil shrinkage will lead to smaller values for the equivalent stock-tank recovery. These calculations also give data showing how the productivity indexes for the producing wells will vary during the reservoir history. Because of decreasing Permeability to the oil and increasing oil viscosity, the productivity index will fall continuously as Production proceeds, and may finally reach values as low as 10 per cent of the initial productivity index. Introduction In a previous paper1 was developed the basic theory for the prediction of the production histories of gas-drive reservoirs. The data required for the application of this theory included the characteristics of the petroleum fluids, such as the viscosity of the Oil and gas phases, the solubility of the gas in the oil, and the oil shrinkage— all expressed as functions of the reservoir pressure—and the permeability-saturation characteristics of the producing rock, as

Jan 1, 1946

By L. C. Raymond

Valuations in the mineral industry differ from those of other enterprises because mines and oil wells have a definite life so cannot be considered a perpetuity. This requires that in any mineral-property evaluation the recovery of invested capital is necessary during the life of the property. Capital writeoffs for nonextractive industries are assumed to be continuously plowed back to sustain the operation and produce yields on the capital invested. The extractive or mineral industry, however, generally attempts to return to the investor both interest and principal during the life of a property. Normally this is done currently and the dividend includes both items. Where the mineral properly possesses large reserves and the life factor approximates a perpetuity, the return on investment is generally comparable to that of industrial stocks. The valuation of a mineral property, at best, is based on educated estimates and judgment factors. This is particularly true as it relates to estimating selling prices over a long term or assessing the quality of management. Also, it is possible to make various assumptions as to rapidity of working out the deposit, varying time for start-up of operations, varying earning rates, so as to obtain different results with the same basic facts. Thus it is not surprising that two engineers, irrespective of their abilities, may not agree exactly even when given the same facts, but their results should be close enough to be used in establishing a fair value for trading purposes. The valuation is no better than the source of basic data and the soundness of judgment factors. Fundamentally the basic principles of mineral valuation are similar for base metals, sulphur, oil, or any other mineral. Each mineral, however, requires an engineer to have a knowledge of such factors as its occurrence, distribution, mining and processing methods, and marketing problems in order to gather and analyze all the facts and data that have a bearing on the earning potential of the property. PRESENT VALUE OF A MINERAL PROPERTY In essence the present value of a mineral property is a sum of money in today's dollars that future earnings from the property are worth. It differs

Jan 1, 1964

By Herbert Clark Hoover, Lou Henry Hoover

QUALITIES which the perfect miner should possess and the arguments which are urged for and against the arts of mining and metallurgy, as well as the people occupied in the industry, I have sufficiently discussed in the first Book. Now I have determined to give more ample information concerning the miners. In the first place, it is indispensable that they should worship God with reverence, and that they understand the matters of which I am going to speak, and that they take good care that each individual performs his duties efficiently and diligently. It is decreed by Divine Providence that those who know what they ought to do and then take care to do it properly, for the most part meet with good fortune in all they undertake; on the other hand, misfortune overtakes the indolent and those who are careless in their work. No person indeed can, without peat and sustained effort and labour, store in his mind the knowledge of every portion of the metallic arts which are involved in operating mines. If. a man has the means of paying the necessary expense, he hires as many men as he needs, and sends them to the various works. Thus formerly Sosias, the Thracian, sent into the silver mines a thousand slaves whom he had hired from the Athenian Nicias, the son of Niceratus1. But if a man cannot afford the expenditure he chooses of the various kinds of mining that work which he himself can most easily and efficiently do. Of these kinds, the two most important are the making prospect trenches and the washing of the sands of rivers, for out of these sands are often collected gold dust, or certain black stones from which tin is smelted, or even gems are sometimes found in them ; the trenching occasionally lays bare at the grass-roots veins which are found rich in metals. If therefore by skill or by luck, such sands or veins shall fall into his hands, he will be able to establish his fortune without expenditure, and from poverty rise to wealth. If on the contrary, his hopes are not realised, then he can desist from washing or digging. When anyone, in an endeavour to increase his fortune, meets the expenditure of a mine alone, it is of great importance that he should attend to his works and personally superintend everything that he has ordered to be done. For this reason, he should either have his dwelling at the mine,

Jan 1, 1950

By T. C. Wilson, Gerald Edmunds, W. M. Peirce, E. A. Anderson

Thirty-six elements have been alloyed singly with cartridge brass. Ammonia and mercury stress-cracking tests have been conducted on the as-rolled and recrystallized strip. Ultra high purity cartridge brass has also been tested. Silicon improves stress- cracking behavior. High silicon (I per cent) cartridge brass quenched from high temperature (for example, 800 C.) annealing is exceptionally resistant to ammonia stress cracking. This improvement is not lost by subsequent cold working, but is greatly reduced by subsequent low temperature annealing. Phosphorus, arsenic, barium, cerium, magnesium, tellurium, tin, beryllium, and manganese benefit stress-corrosion resistance under some circumstances, but not others. The other alloying additions tried had no large effect on stress-cracking resistance. None of the elements added accelerated stress cracking. The impurities in commercial brass are not responsible for season cracking.

Jan 1, 1945

By W. L. McMorris, A. H. Brisse

IN the last several years the coal industry has intensified its effort to solve the growing problem of cleaning and recovering fine mesh coals. On one hand there has been increasing civic pressure for cleaner streams, and on the other hand there has been increasing production of fine mesh coal, resulting directly from adoption of the modern mining methods so essential to the economy of the coal mining industry. Cleaning fine coal with the same precision possible with coarser coals is a difficult task, and for coals finer than 200 mesh it has been impractical. Furthermore, the inclusion of -200 mesh material in the final product markedly increases costs of dewatering and thermal drying, which are necessary steps if coal is to meet market requirements. Consequently these extreme fines have generally been wasted. As a result, problems have been created in many districts because there has not been enough area for adequate settling basins.

Jan 2, 1958

By D. T. Peters, C. R. Cupp

Aging of commercial 18 pct Ni maraging steel and of related binary, ternary, and quaternary alloys has been studied by electrical resistivity, X-ray diffrac-tion, and hardness measurements. The aging process is in three stages: 1) recovery of martensite; 2) two precipitation reactions; 3) formation of nickel- rich austenite. The main objective of this work was to discover the nature of the Co-Mu interaction. Addition of cobalt to the Fe-18 pct Ni-5pct Mo alloy results in acceleration of the pvecipitation reaction by increasing the super-sat~lration 0f molybdenum. The cobalt-containing al- loys show no incubation period for the precipitation reaction, but the alloy without cobalt shows an initial slow reaction. These results are interpreted in terms of precipitation on dislocations. At low aging temperatures, the presence of cobalt leads to the appearance of a second type of precipitate which is a particularly effective hardener. Cobalt was found to retard the formation of austenite. Overaging is a combination of classical overaging and the formation of austenite in the structure. he- activation energy for the precipitation reaction determined from resistivity ,measurements is 42.8 kcal per mole and the growth of the precipitate is found to obey at law at high tenzperatures and a tU3 law at low temperatures. HE mechanism of strengthening of the 18 pct Ni maraging steels has been studied extensively since 1962.'-? The strengthening is due to precipitation hardening of the martensitic matrix. The main precipitate is an inter metallic compound involving molybdenum, but there is disagreement about its identity.

Jan 1, 1967

By Benjamin Lustman, Robert F. Mehl

The study of the high-temperature oxidation of pure metals, intensively pursued experimentally since the pioneer work of Pilling and Bedworth1 and supplemented by the recent theoretical work of Wagner2 is now well advanced. The important field of low-temperature oxidation—i.e., oxidation extending only through the temper color range of thicknesses with the formation of thin oxide layers in the range from 0 to 1000-2000 ?ngstroms—has not, however, reached so satisfactory a state, owing largely to the experimental difficulties that attend the formation and study of thin films; most of the work has been performed on abraded specimens whose surface irregularities approximated the thickness of the films formed. It has been pointed out that the rates of oxidation of different crystal faces are different and that the difierence may be related to the orientation relationships that obtain between the metal crystal and the superimposed oxide crystal; it has also been suggested that this orientation dependence should manifest itself in rates of oxidation and perhaps also of corrosion in aggregates bearing preferred orientations.3'4 An attempt to measure the rates of oxidation of different crystal faces of alpha iron demonstrated this difference in rate,4 but the dependence of rate on orientation was not simple; the method of measuring thickness, consisting of a color comparison with barium stearate multi-films of known thickness, was not wholly satisfactory. For these reasons it was felt that a study of the rate of oxidation of single crystals prepared with surfaces as smooth as possible, using a sensitive method giving true film thickness, should be profitable. Copper was chosen because of the ease of reduction of the primary oxide film and because the orientation relationships between metal and oxide and the composition of the oxide films formed at low temperatures are known; for thin films formed at low temperatures, Cu2O alone occurs.22-24 Experimental Procedure Various methods of surface preparation were attempted in order to obtain a surface that would oxidize uniformly and repro-ducibly. Electrolytic polishing by the method of Jacquet5 and electrolytic and mechanical polishing followed by annealing in vacuum and in purified hydrogen at various temperatures were tested. The procedure finally adopted consisted in a fine metallographic polish followed by an anneal in purified hydrogen at temperatures of 900° to 1000°C. for 12 hr. or more. The surface so produced was very bright and smooth, with no trace of specular etching (though some grain-boundary etching was observed); indeed, fine scratches produced by the final polish were entirely removed by the high-temperature anneal. After this treatment, the specimens were cooled in hydrogen to room temperature and placed in the oxidation furnace, where

Jan 1, 1941

By Benjamin Lustman, Robert F. Mehl

The study of the high-temperature oxidation of pure metals, intensively pursued experimentally since the pioneer work of Pilling and Bedworth1 and supplemented by the recent theoretical work of Wagner2 is now well advanced. The important field of low-temperature oxidation—i.e., oxidation extending only through the temper color range of thicknesses with the formation of thin oxide layers in the range from 0 to 1000-2000 ?ngstroms—has not, however, reached so satisfactory a state, owing largely to the experimental difficulties that attend the formation and study of thin films; most of the work has been performed on abraded specimens whose surface irregularities approximated the thickness of the films formed. It has been pointed out that the rates of oxidation of different crystal faces are different and that the difierence may be related to the orientation relationships that obtain between the metal crystal and the superimposed oxide crystal; it has also been suggested that this orientation dependence should manifest itself in rates of oxidation and perhaps also of corrosion in aggregates bearing preferred orientations.3'4 An attempt to measure the rates of oxidation of different crystal faces of alpha iron demonstrated this difference in rate,4 but the dependence of rate on orientation was not simple; the method of measuring thickness, consisting of a color comparison with barium stearate multi-films of known thickness, was not wholly satisfactory. For these reasons it was felt that a study of the rate of oxidation of single crystals prepared with surfaces as smooth as possible, using a sensitive method giving true film thickness, should be profitable. Copper was chosen because of the ease of reduction of the primary oxide film and because the orientation relationships between metal and oxide and the composition of the oxide films formed at low temperatures are known; for thin films formed at low temperatures, Cu2O alone occurs.22-24 Experimental Procedure Various methods of surface preparation were attempted in order to obtain a surface that would oxidize uniformly and repro-ducibly. Electrolytic polishing by the method of Jacquet5 and electrolytic and mechanical polishing followed by annealing in vacuum and in purified hydrogen at various temperatures were tested. The procedure finally adopted consisted in a fine metallographic polish followed by an anneal in purified hydrogen at temperatures of 900° to 1000°C. for 12 hr. or more. The surface so produced was very bright and smooth, with no trace of specular etching (though some grain-boundary etching was observed); indeed, fine scratches produced by the final polish were entirely removed by the high-temperature anneal. After this treatment, the specimens were cooled in hydrogen to room temperature and placed in the oxidation furnace, where

Jan 1, 1941

By William Johnson

IT is now recognized that several important types of reactions in metallic systems proceed by the formation of nuclei and the growth of these nuclei. The process, of freezing is a simple example of this, as Tammann pointed out years ago.1Tammann held that the rate of freezing is determined by a rate of nucleation, expressed as the number of nuclei formed per unit volume of unfrozen liquid per second, and a rate of growth of these nuclei, expressed as the linear rate of radial growth in units of length per second. For isothermal freezing the conception is simple; for ordinary freezing, extending over a range of temperature, it is not as simple, for the values of the two constants must change with change in temperature. There is ample evidence that the postulated mechanism is correct even though a quantitative derivation of the rate of isothermal or of ordinary freezing in terms of the two constants has been lacking. In recent years other reactions have been found to proceed in a similar fashion. It has been well established, particularly by Bain,2-8 that the formation of pearlite from the eutectoid decomposition of the solid solu-tion austenite proceeds in such a way, and Polanyi and Schmid, Tammann and Crone, Parnop and Sachs, and others'-1 have shown that the process of recrystallization proceeds in a similar way. Isothermal reaction rates have been determined for eutectoid decom-position by a number of investigators. Bain's2-8 work on the formation of pearlite from austenite is especially valuable in this respect-the type of isothermal reaction curve obtained, as illustrated in Fig. 13, showed an initial slow rate, accelerating to an intermediate maximum rate which then decelerated to the completion of the reaction; similar curves have been obtained by Wever and his collaborators.' Other eutectoid decompositions show similar behavior: for example, the decomposition of the beta eutectoid in the copper-aluminum system, studied by Smith

Jan 1, 1939

By W. L. Martin, J. N. Dew, H. B. Steves, M. L. Powers

This paper presents and discusses the results obtained during a pilot test in the Loco field in southern Okla homa. The test was conducted in a 2%-acre pattern that was part of a 20-acre conventional waterflood pilot area. The conventional flood was well past its economic limit when the hot waterflood was initiated to obtain technical information and operating experience. Temperature data from nine observation wells showed that about 75 percent of the pattern was affected by heat, and that heat losses were severe in the pilot pattern. About 60 percent of the injected heat was lost to overburden and underburden zones during hot-water injection. Wellbore heat losses were held at tolerable levels at the shallow depth of the test by providing a low-pressure air annulus between the injection tubing and well casing. Hot water provided water injectivity increases of 200 to 400 percent. The hot water channeled across the lower portion of the oil sand in three directions through zones of relatively high water saturation. There was no conclusive evidence that natural fractures or pressure partings aflected the flow of fluids in the pilot pattern; however response undoubtedly was aflected by localized pressure gradients and by injection-production rate ratios. The results showed that hot waterflooding increased oil recovery in a reservoir containing 600 cp oil. The total tertiary oil production from the pilot pattern area was 3,896 bbl or about 156 bbl/acre-ft swept by heat. The corre.sponding WOR was about 34:I. Description of the Hot Waterflood Process To hot waterflood an oil reservoir, water is injected that has been heated to a temperature substantially higher than the original reservoir temperature, but lower than the vaporization temperature of water at the prevailing pressures. In the reservoir the hot water flows continuously into cooler sand and rapidly loses heat to the sand until it has been cooled to the original reservoir temperature. Thus, a heated zone and a region or "bank" of cooled water begins to accumulate immediately after hot water injection is started. This bank of cooled water continues to grow ahead of the heated zone, which also grows, but at a slower rate. This occurs because heat transfer is almost instantaneous, and the ratio of heat capacities of water to rock is such that two or three unit PV of hot water must be injected to heat a given unit bulk volume of the reservoir. The primary displacement mechanism is the same for both hot and conventional cold waterfloods; i.e., "piston" displacement occurs at the original reservoir temperature. The incremental benefits of hot waterflooding usually occur long after the breakthrough of cold water at producing wells, and the increased oil recovery necessarily is accomplished with high WOR's (water-oil ratios). Heat decreases the viscosity and density of oil and water. These effects result in more rapid and increased recovery of secondary or tertiary oil. If the cost of the required heat is low enough, the ultimate oil recovery of a hot waterflood should be increased substantially over what would be expected at the economic limit of a conventional cold waterflood. The economic benefits of any hot-fluid injection project depend primarily upon the cost of the heat required to produce more oil at an increased rate. This cost depends in part upon the amount of heat lost to surrounding formations. Heat loss depends upon reservoir thickness, water injection rate and temperature, the depth of the formation, well spacing, and the characteristics of the reservoir rock and surrounding formations. In general, percentage heat losses decrease as injection rate and reservoir thickness increase. Although it is an old idea, hot-water injection has not received widespread field application in the oil industry as a drive process. Much of the original field work with hot water was done in Pennsylvania fields where water permeabilities and injection rates are low. In these cases, hot-water injection was used primarily as a means of increasing in-jectivities — not as a recovery process. Ramey' recently has published an excellent review of the development of hot fluid injection processes. Recent publications"' and our own experiences now indicate that hot water or steam injection also can effectively increase the oil recovery from reservoirs containing viscous crudes. However, the economics of these methods as displacement processes have not been established. Several theoretical predictive techniques have been published (for a review see Ramey'), but simplifying assumptions make

Jan 1, 1969

By F. V. Lenel

Resistance sintering under pressure is a method of hot pressing in which a powder compact is subjected to pressure and simultaneously heated by passing a low voltage high amperage current through it. Equipment for this process is described. Its basic characteristics such as resistance requirements for powders and compacts, temperature distribution in compacts, and gas reactions during resistance sintering are discussed. Examples of the sintering process in compacts made of a single metal or an alloy powder and in compacts made of mixtures of powders are presented. Potential commercial applications of the process are evaluated. THE usual sequence of operations in commercial powder metallurgy is to compact metal powders in a die at room temperature and sinter the compact subsequently without applying pressure while the compact is in the sintering furnaces. In hot pressing, on the other hand, the compacting and the sintering are combined. The loose powder, or in many cases a cold formed compact, is inserted into the die which is held at the hot pressing temperature, the compact is left in the die until it attains its temperature, and then pressure is applied and maintained for a given length of time. The die may be heated by surrounding it with a suitable furnace, by high frequency induction heating, or by passing current through the die. In hot pressing, compacts of high density and good mechanical properties can be produced in a relatively short time. One of the principal difficulties in hot pressing is the lack of suitable die materials which will have adequate strength at the hot pressing temperature. This difficulty can be overcome at least partially by heating only the material to be hot pressed without heating the die directly. This can be done by passing a low voltage high amperage current through the material and simultaneously subjecting it to pressure. Either loose powders or compacts can be hot pressed by this method in which the desired temperature is produced by the power dissipated in the metal powder. This method of hot pressing has been termed "electrical resistance sintering under pressure." The most significant differences between this operation and conventional hot pressing are: 1—The sintering times are very short, usually a fraction of a second and at most a few seconds. 2—The powder and die are initially cold. 3—Heat is generated within the powder itself and not conducted in from the die. 4— The pressure used is high. 5—Cooling following sintering is rapid, amounting to a quench. Resistance sintering of metal powders under pressure has been suggested repeatedly. In 1933, G. F. Taylor' proposed an apparatus which consisted of an insulating tube made of glass, or a ceramic filled with the powder to be pressed, and plungers above and below the powder. The powder was to be heated by passing an electric current through it and pressure was then applied. The apparatus was intended principally for hot pressing cemented carbides. Although the principle of resistance sintering under pressure is clearly shown in this patent, few details are given. A sintering period of a second or a fraction of a second, which is terminated by the operation of an inertia switch, is mentioned but no values for current density are mentioned. Low pressures, such as atmospheric pressure or a somewhat higher pressure exerted through a lever, are suggested. W. D. Jones' discussed electrical resistance sintering under pressure and proposed using resistance welding apparatus for this purpose. In a patent issued in 1944, G. D. Cremera described a method of electrical resistance sintering under pressure using resistance welding apparatus which was to be applied mostly to nonferrous metals such as copper, brass, bronze, and aluminum. Current densities of 400,000 amp per sq in., sintering times of 1 and 2 cycles of 60 cycle current, and pressures of 5 to 10 tsi are proposed. Cremer suggested using an

Jan 1, 1956