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By Frank Foote, V. H. Nordstrom, Eric R. Jette, Bernard Queneau

The nickel-chromium alloys form the base for many industrial heating alloys, so that this system is of considerable practical importance. The literature on these alloys, however, contains much conflicting evidence, not only regarding the solubility limits of the terminal solid solutions at different temperatures but even regarding the number of phases existing in the system. Part of the difficulty undoubtedly arises from the fact that chromium of sufficiently high purity has been available only during the last few years. A second and possibly even more important difficulty arises from the ease with which chromium reacts with silicon and carbon compounds and the atmosphere to form silicides, carbides, nitrides and oxides. Pilling and Kihlgrenl in 1929 reviewed the existing scanty information. They did not consider the diagram by which they summarized the various bits of information to be entirely satisfactory. Matsunaga2 investigated the system by thermal analysis, microscopic examination and other means. Electrolytic nickel of 99.9 per cent purity and thermit chromium containing 0.30 per cent Al, 0.40 per cent Fe, 0.25 per cent Si and 0.04 per cent C were used. A Tammann furnace with hydrogen flowing through it was used for melting. Sekito and Matsunaga3 reported an X-ray investigation, presumably on these same alloys, which, as far as can be judged from the abstract, essentially confirmed the thermal and microscopic results. Nishigori and Hamasumi4 found compositions for the terminal solid solutions in equilibrium at the eutectic temperature which agreed fairly

Jan 1, 1934

By T. L. Berger, M. C. lnman, M. F. Rose

AFTER shock loading, mechanical twinning has been observed by several authors1-4 for a variety of fcc metals and alloys. It has been shown2,3 that low stacking fault energy materials deform primarily by the formation of mechanical twins and stacking faults during dynamic loading. Further, Inman, Murr, and Rose2 have shown that a correlation exists between the average hardness and the volume percent of mechanically twinned material in stainless steel. It has been observed in nickel' that mechanical twins are produced during shock deformation if the peak pressure associated with the shock wave is greater than 350kbar. It is the purpose of this work to discuss shock-hardening mechanisms in nickel and to determine to what extent the initial condition influences the final response. The "flying plate technique" was used to generate planar shock waves with peak pressures as high as 710 kbar. The details of the technique5" have been discussed elsewhere and will not be repeated here. The material used in this study was polycrystalline nickel of 99.98 pct purity and had an initial grain size of 0.18 mm. Prior to any deformation, all samples were given a stress-relief anneal of 6 hr at 600°C in a vacuum furnace. After annealing, the initial condition of the samples was changed by cold rolling individual samples from 0 pct to a maximum of 80 pct reduction in thickness. This provided samples with controlled initial histories for shock deformation. Immediately after shock loading, the specimens were slowed and quenched by suitable arrangement of buffer material and water bath. This technique minimized specimen damage and the effects of shock heating on the samples. Since deformation twins in high stacking fault energy fcc metals are only produced at high stress levels, the initial defect configuration prior to mechanical twinning should greatly influence the number of twins formed. In fact, Zukas and Fowler7 have found that prestraining in iron and steel greatly suppresses the formation of mechanical twins during the shock deformation process. Following the methods of Warren and warekois8 and Cohen and Wagner,9 X-ray diffraction profile analysis was performed to determine the incidence of stacking faults and mechanical twins in the deformed nickel. Analysis was made on samples in the annealed, cold-rolled, shock-loaded, and cold-rolled—shock-loaded states. The estimated accuracy of the peak position measurements is *0.01 deg in 2?. Therefore the accuracy in the measurement of the relative peak shifts between the (400) and (222) diffraction line profiles is on the order of *0.04 deg in 2?. None of our measurements indicated peak shifts greater than 0.04 in 28. This would correspond to a fault density of -1 pct and sets the limit on the sensitivity of our instrument. Similarly, analysis of the shift in the center of gravity of the diffraction line profiles yields the minimum measurable value of the twin fault probabilitya to be -0.002. Fig. 1 shows mechanical twinning in nickel shock-loaded to 400 kbar. In this photograph, fault intersections are clearly visible. The thickness of the individual fault lamellae was determined from the image widths of their lines of intersections by the

Jan 1, 1968

By R. M. Waterstrat

The phases occurring in the V-Mn system were studied by means of X-yay diffraction and metallo-paphic techniques, using are-melted alloy specimens annealed in the temperature range 800° to 1150°C and quenched. The bcc solid solution extends at 1250°C all the way from vanadium to 6-manganese. Below 1050°C the a-phase is formed, and the terminal a-manganese phase is stabilized up to about 900°C by vanadium in solid solution. IN the only previous general survey of the V-Mn system Cornelius, Bungardt and Schiedtl reported the existence of three intermediate phases corresponding to the approximate compositions VMn,, VMn, and V5Mn. The phase VMn8 has recently been identified as a o phase2 but the alloy VMn was found to have a bcc structure2 corresponding apparently to the vanadium solid solution rather than to the large cubic unit cell reported by Cornelius et al. 1 Subsequent work by Rostoker and Yamamoto3 has shown that the vanadium-base bcc solid solution extends to at least 15 pct Mn at 900°C. An alloy corresponding to the composition VMn, was examined by Elliott,4 who reported that the as-cast sample as well as samples annealed at 1200o and 1300°C had bcc structures, but that annealing at 1000°, 800") and 600°C produced two phases. One of these phases was apparently the bcc solid solution and the other resembled the o phase structure. Hellawell and Hume-Rothery5 established the phase relationships in manganese-rich alloys above 1000°C, and showed that the o phase in this system is replaced by the 6 Mn (bcc) solid solution at temperatures above 1050°C. These results suggest that a continuous bcc solid solution may exist above 1050°C between vanadium and 6 Mn. The present investigation was undertaken in order to develop more complete information in regard to this system. EXPERIMENTAL METHODS The alloys used in the present work were prepared by arc-melting electrolytic manganese having a minimum purity of 99.9 pct and vanadium lumps with a purity of 99.7 pct. The major impurities present in these metals were carbon, nitrogen, and oxygen and this would account for the small percentage of nonmetallic inclusions observed metal-lographically. The arc-melting was at first performed under a helium atmosphere and it was necessary to keep the melting times as short as possible in order to minimize the loss of manganese by vaporization. It was later found that the evaporation of manganese was considerably reduced when the melting was done under argon atmosphere. The final composition of each alloy was calculated by assuming that the total weight loss during melting was due to evaporation of manganese. Compositions which were calculated in this manner agreed reasonably well with the results of chemical analysis, as shown in Table I. Spectrographic analysis revealed the presence of contamination by tungsten, but in no case was the percentage of tungsten greater then 0.4 at. pct. The specimens were in each case broken in half and the fractured section was examined visually and microscopically for evidence of inhomogeneity. Each specimen was homogenized at temperatures near l100°C, as shown in Table I. After this treatment most specimens consisted of large columnar grains of the bcc vanadium solid solution. The etchant used in most of the metallographic work consisted of 20 pct nitric acid, 20 pct hydro-flouric acid, and 60 pct glycerine. It was found that this etchant would clearly delineate the phases present in these alloys although it does not produce any striking contrast between the phases. For certain manganese-rich alloys, a 1 pct aqueous solution of nitric acid was used. This etchant gave a brown color to the a-manganese phase, whereas the o phase was virtually unattacked and appeared very light as shown in Fig. 1. The etchants used by Cornelius et a1.l were found to produce spurious effects in some of these alloys. In particular, the vanadium-rich alloys etched in hot sulfuric acid often appeared to consist of two phases when both X-ray diffraction and etching with the glycerine-acid mixture indicated the presence of single phase bcc solid solution. A few percent of what appears to be an oxide or nitride phase was found at the grain boundaries and in the interior of the grains, especially in the vanadium-rich alloys. All alloys were annealed in sealed silica tubes containing 1 atm of pure argon and these tubes were then quenched in cold water. Although some manganese loss occurred during annealing, the loss seemed to be confined to the surface of the speci-

Jan 1, 1962

By H. C. Chao, W. F. Hosford, L. H. Van Vlack

The negative "plastic Poisson's ratio" suggested in earlier studies of Mus deformation is analyzed, and the results are verified experimentally with NaCl crystals. In the early stages of deformation where the primary {110}(110) slip predominates, compression along. the [001] direction produces contraction along the lateral [011] direction plus a compensating expansion along. the [100] direction. With additional strain, the primary slip is supplemented by secondary {111}(110) slip so that the above contraction diminishes and a more typical deformation appears. THE shape change of bee and fee crystals deformed by compression or tension along [011] has been analyzed in some detail and shown to be responsible for the development of peculiar microstructures in [011] fiber textured polycrystals of these metals.1'3 This paper concerns the unusual shape change accompanying [011] compression of NaCl crystals. It is the direct outgrowth of an earlier investigation of the deformation of manganese sulfide inclusions in steel.3,4 In that investigation, cylindrical specimens of steel containing small oriented crystals of MnS were prepared by powder metallurgy and plastically compressed. The flow of the inclusions was determined relative to that of the steel by sectioning the composite and measuring the length-to-width ratio L/W of the inclusion and diameter-to-height D/H ratio of the steel cylinder on the plane of section. These L/W ratios, normalized by dividing by the initial LO/WO ratio of the inclusion, were compared with the normalized D/H ratio of the steel cylinder. Of particular interest here are the deformation characteristics of an inclusion oriented with [Oil] parallel to the compression axis. When measurements were made on sections parallel to the (100) plane of the inclusion, the L/IV ratios were only slightly in excess of unity, indicating a high apparent hardness of the [011] criented inclusion. However, measurements on a (011) plane of section resulted in L/W ratios which were much larger, Fig. 1. These observations prompted an analysis of the strains resulting from slip in an MnS crystal compressed along [011.]. CRYSTALLOGRAPHIC ANALYSIS Manganese sulfide has the NaCl crystal structure, and the predominant slip system is {110}(110). A secondary system, {111}(110), has also been reported.= {110}(110) Slip. When a crystal is subject to a uni-axial compressive stress 011 along [011], four slip systems, (101)[101.], (101)[101.], (110)[i10], and (110) [ 110], will be equally stressed with a shear stress t = 0.2 011 while the other two {110}( 110) systems will be unstressed. The normal strain En along any reference axis n resulting from slip is given by Schmid's law: en = S COS ?in COS in ?i 111 where ?in and +in are the angles between n and the i slip direction and n and the i slip plane normal, respectively, and where ?i is the shear strain on the i slip system, For the four active slip systems above, the cos ?in cos +in terms are all equal when the reference axes are the [011] compressive axis, [011] and [ 100]. Eq. [I.] therefore reduces to en - cos ?n cos +ny [2] where y =S?i for all slip systems. Substituting the appropriate angles, Eon = 0.25? 110 eon - 0.25y110 [3] €100 = -0.50y 110 The interesting feature of Eqs. [3] is that they predict that the strains in the [011] and [011] directions, resulting from {110}(110) slip, are equal and of the same sign. Thus when a crystal is compressed along [011], it will contract along the lateral [oil] direction

Jan 1, 1967

By John Chipman, Theodore B. Winkler

IN order to understand more fully the complexities of the reactions occurring between the liquid steel and the slag in the basic open-hearth steelmaking furnace, investigations in this country and abroad have turned to laboratory equilibrium studies. This paper is one of a series of reports on investigations being conducted at the Massachusetts Institute of Technology. The experimental work was completed early in 1942. The slag systems found in the basic open hearth are very complex, being made up of at least eight major components and as many others whose effect might be classified as minor. The first two papers of the series, by Fetters and Chipman,l,2 as well as the paper by Taylor and Chipman,3 dealt with the simplest possible slag system that would resemble those found in the basic open hearth-the slag system consisting of CaO-MgO-SiO2-FeO. (Taylor's rotating induction furnace eliminated the necessity of contamination of the slag by MgO.) Having arrived at some reasonable conclusions regarding the physical chemistry of the reactions between molten iron and the simple slags at equilibrium, the next step was to investigate more complex slag systems. The major purpose of the present investigation was to determine what factors control the distribution of phosphorus between molten iron and the more complex basic slags at equilibrium, and to what extent these factors are influential. The slags used contained CaO, MgO, Si02, FeO, Fe203, P205, MnO, A1203 and CaF2, but not all of the slag samples contained all of these components at one time. REVIEW OF LITERATURE Although a number of interesting papers have been published on the subject of dephosphorization of an iron bath, there are as yet no results from laboratory studies that give thoroughly reliable information on the dephosphorization reaction. Even for the supposedly simple Fe-O-P system involving iron-phosphorus melts and iron oxide-iron phosphate slags, the experimental results are contradictory and no formulas have been established that adequately fit the equilibrium conditions. The Fe-O-P system has been studied by Schackmann and Brings4' von Samson-Himmelstjerna,5 Oelsen and Maetz,6 Bischof and Maurer,7 Diepschlag and Schürmann,8 and Herty,9 and the results of their investigations appear in Table I. A number of different equilibrium constants and distribution ratios

Jan 1, 1946

By Frank Foote, E. R. Jette

In recent years the constitution of the high-silver aluminum-silver alloys has been extensively investigated. Hansenl has reviewed the literature to 1935. More recently, Obinata and Hagiya,2 Hofmann and Volk,3 Taziri4 and Tishchenko5 have confirmed the general features of the phase diagram in the region around 25 atomic per cent aluminum. In this paper we present the results of high-precision measurements of lattice constants of the silver-rich alpha solid solution in the homogeneous range and the neighboring two-phase regions. These results are used to establish the nature of the solid solution, the identity of directly measured densities with those calculated from lattice constants and the homogeneity limits of the alpha solid solution with respect to three different neighboring phases. A study of the earlier investigations indicated that the last two subjects in particular required new and accurate data. Experimental Procedure Preparation of the Alloys.—The alloys were made from high-purity silver and aluminum. The silver was "Proof Silver," 99.999 per cent pure, supplied by the U. S. Metals Refining Co. The aluminum was 99.97 per cent pure (contained Si, 0.009 per cent; Fe, 0.0016 per cent; Cu, 0.004 per cent) and was supplied by the Aluminum Company of America. The lattice constants of these two materials have been reported by Jette and Foote.6 Weighed amounts of the two metals were placed in alundum crucibles and melted in vacuo in a high-frequency induction furnace. The melts were allowed to cool in the crucible, the ingots thus obtained weighed about 10 grams. These ingots were then filed clean, hamered, again cleaned and given a homogenizing anneal in vacuo of from 6 to 15 days at temperatures ranging from 500" to 695°C. The ingots were air-cooled from the annealing temperature. Lattice-constant Measurements.—Carefully prepared filings for X-ray analysis were sealed into evacuated quartz or Pyrex tubes and annealed for various periods of time at suitable temperatures. The furnaces used were vertical, rapid-quenching furnaces, the samples being quenched by crushing the sample tube under water by means of a heavy plunger. The general X-ray technique has been previously described6 The cameras were of the symmetrical, back-reflection, focussing type. Ka, radiation from a cobait-nickel alloy target was used. The wave-length values were taken from the second edition of Siegbaum's book.7 A correction for the index of refraction was applied and the lattice constants were calculated by the method of Cohen.8, 6 The lattice constants were calculated to a common temperature of 25°C., using the value of the linear expansion coefficient of pure silver as 18.9 X 10-6. Presumably the expansion coefficient for

Jan 1, 1941

By Frank Foote, E. R. Jette

In recent years the constitution of the high-silver aluminum-silver alloys has been extensively investigated. Hansenl has reviewed the literature to 1935. More recently, Obinata and Hagiya,2 Hofmann and Volk,3 Taziri4 and Tishchenko5 have confirmed the general features of the phase diagram in the region around 25 atomic per cent aluminum. In this paper we present the results of high-precision measurements of lattice constants of the silver-rich alpha solid solution in the homogeneous range and the neighboring two-phase regions. These results are used to establish the nature of the solid solution, the identity of directly measured densities with those calculated from lattice constants and the homogeneity limits of the alpha solid solution with respect to three different neighboring phases. A study of the earlier investigations indicated that the last two subjects in particular required new and accurate data. Experimental Procedure Preparation of the Alloys.—The alloys were made from high-purity silver and aluminum. The silver was "Proof Silver," 99.999 per cent pure, supplied by the U. S. Metals Refining Co. The aluminum was 99.97 per cent pure (contained Si, 0.009 per cent; Fe, 0.0016 per cent; Cu, 0.004 per cent) and was supplied by the Aluminum Company of America. The lattice constants of these two materials have been reported by Jette and Foote.6 Weighed amounts of the two metals were placed in alundum crucibles and melted in vacuo in a high-frequency induction furnace. The melts were allowed to cool in the crucible, the ingots thus obtained weighed about 10 grams. These ingots were then filed clean, hamered, again cleaned and given a homogenizing anneal in vacuo of from 6 to 15 days at temperatures ranging from 500" to 695°C. The ingots were air-cooled from the annealing temperature. Lattice-constant Measurements.—Carefully prepared filings for X-ray analysis were sealed into evacuated quartz or Pyrex tubes and annealed for various periods of time at suitable temperatures. The furnaces used were vertical, rapid-quenching furnaces, the samples being quenched by crushing the sample tube under water by means of a heavy plunger. The general X-ray technique has been previously described6 The cameras were of the symmetrical, back-reflection, focussing type. Ka, radiation from a cobait-nickel alloy target was used. The wave-length values were taken from the second edition of Siegbaum's book.7 A correction for the index of refraction was applied and the lattice constants were calculated by the method of Cohen.8, 6 The lattice constants were calculated to a common temperature of 25°C., using the value of the linear expansion coefficient of pure silver as 18.9 X 10-6. Presumably the expansion coefficient for

Jan 1, 1941

By W. C. Ellis, M. E. Fine

In the iron-cobalt system there are several property-composition relationships of theoretical importance. The alloys are ferromagnetic exhibiting a maximum saturation at approximately 33 at. pct cobalt;' the interatomic distances at room temperature show large positive deviations from Vegard's rule;2 and in the region of 50 at. pct cobalt there is an order-disorder transition2 which has a large effect on other properties. The thermal expansion data for the system have been reported only from room temperature to 100 C and for this temperature range a minimum in coefticient in the rcgion of 50 at. pct cobalt is well established.3,4,6 This paper reports the expansion properties in the iron-cobalt system for temperatures from 30 to 850°C, shows the correlation with other physical properties, and proposes an explanation for the tcrrelation. Experimental Procedure The thermal expansivities of iron-cobalt alloys in 10 pct steps in composition were determined from 30 to about 850°C. The major series of alloys was prepared by induction melting from Armco iron and cobalt rondelles with the addition of about 0.6 wt pct manganese. This series was supplemented by three compositions: high purity electrolytic iron, high purity electrolytic cobalt, and an alloy of 52.1 wt pct cobalt prepared from the high purity electrolytic iron and electrolytic cobalt by vacuum-melting. The compositions of both series of alloys are given in Table I. The specimens for measurement were prepared from the cast ingots by first hot-swaging followed in most instances by cold-swaging to 0.180-in. diam rod. Some alloys in the region of 5c pct cobalt, because of inherent cold-brittleness, were swaged hot to the final diameter. The expansion specimens were approximately 2 1/2 in. long with flat-ground and polished ends. Before measurement they were annealed in hydrogen for I hr at 900°C. In the apparatus used for the thermal expansivity measurements (Fig I), a modification of that designed by Hidnert and Sweeney,? the differential expausion between the specimen and vitreous silica was measured by a dial micrometer reading to 0.001 mm. An invar fixture supported the dial gauge, and this fixture, in turn, was connected to a split invar collar which supported the outer silica tube. A pyrex "T" was placed over the outcr silica tube and was sealed to the invar collar by Apiezon Q sealing compound. A movable hollow vitreous silica rod which rested on top of the test specimen slid through a flexible rubber diaphragm cemented to the top of the pyrex "T." The specimen rested On a vitreous silica pedestal fused into the outer tube and was kept centered by a silica sleeve. A nonoxidizing atmosphere was obtained by admitting hydrogen into the

Jan 1, 1949

By Edward Keller

In a paper, " A Study of the Elimination of Impurities from Copper-Mattes, etc.," presented to the Institute at the Atlantic City meeting, February, 1898, I gave certain figures which I called the relative slaggability in refining copper. In that paper* will be found the following pertaining to this subject: Relative Slaggability in Refining Converter-Copper. Cu. Pb. Bi. Sb. As. Se, Te. 1 129.5 1.13 7.30 5.22 0.81 and Relative Slaggability in Refining Electrolytic Copper. Cu. Pb. Sb. As. 1 41 9.97 7.13 Since there is a, possibility of misinterpretation of the above values, the following supplementary information may seem justified in explanation. As the contents of impurities in the unrefined or crude copper were unknown, the contents of the refined copper were substituted therefor, merely in order to obtain the two series of figures for comparison. These figures are higher than they would be had I been able to take the correct ones for the unrefined copper. The high figure, 129.5, for lead, in the case of converter-copper, means simply that more lead was slagged from the crude copper than remained in the refined copper; or, in definite values, that to 1 per cent. of copper slagged, the ratio of the lead gone into the slag and the lead remaining in the refined copper is 129.5 : 100. It is possible to approximate the true slaggability much more closely by adding the quantities of impurities in the refined copper to those in the slag, thus obtaining values for the crude copper in which the amounts volatilized are ignored (the latter

Jan 1, 1901

By R. Ward Grosz

Reasonable and timely solutions to the complicated mathematical calculations involved in the mine planning, economic evaluation and slope stability studies related to the Ruth Mine would not have been feasible without the modern digital computers. The Ruth Mine was a prosperous underground copper operation in east central Nevada from 1915 to 1948, when rising mining costs finally exceeded the value of the ore. A substantial reserve of porphyry copper remained in the ground, but until recently all economic evaluations indicated that it was at best a marginal operation and a relatively poor risk of capital. There has been a steady progress in improving all aspects of surface mining since the first steam shovel started stripping overburden; however, developments in just two rather specialized areas proved to be critical in changing the Ruth Mine from a reserve of mineralized rock to an economically attractive orebody. One involved the progress made in recent years in the science of slope stability. Applying the latest techniques in this field to mine planning resulted in reducing the stripping ratio from 6.0:l to 4. 2:l. The other major factor was the efficiency and cost performance of large capacity haulage trucks which made it feasible to go down over 1100 ft. in an open pit and recover ore with a high stripping ratio economically.

Jan 1, 1969

By E. T. Turkdogan

This is a compilation and a critical review of the data on the Fe-Ca-0 ternary system. Using the results on the reductiorz-equilibria, an oxygen potential diagram is drawn for the greater part of the system. A number of univariant systems and invariant points, not determined experimentally, are evaluated by making use of the theorem on univariant curves intersecting at an invariant point. The formation of solid solutions and ternary compounds and the crystal structures of some of the phases in the composition-diagram are given for a feu! temperatures. DURING the past thirty years there has been a continued interest in the study of the Fe-Ca-0 system. A detailed literature survey made by white1 in 1943 indicated that further work was required to clarify the phase relationships; in fact, the work carried out in the subsequent years, reviewed by Burdese2 in 1954, made a valuable contribution to a better understanding of this subject. Most of the data were obtained by the step-wise reduction of mixtures of iron oxides and calcium ferrites. However, there is some uncertainty about the phase relationships in this system, arising mainly from insufficient use of thermodynamic concepts in the construction of phase diagrams. In this paper an attempt is made to establish the invariant points from the available data. OXYGEN POTENTIAL DIAGRAM Schenck and coworkers3,4 were the early investigators who studied part of this system by the step- wise reduction method and suggested the formation of two ternary compounds, CaO.FeO.Fe2O3 and 2Ca0.5Fe0.2Fez03, the latter being referred to as point X. They also deduced from their results that the phases Y (8.74Ca0.32.5Fe0.8.74Fe2O3 and Z (2.02CaO-97.98FeO) were formed near the w?stite corner of the system. Martin and voge15 postulated the existence of the compounds CaO.9FeO and 4Ca0.3Fe3O4; the former is very close to the composition of point Z and the latter to that of CaO.FeO-Fe2O3. The most valuable contribution to the presen knowledge on this system was made by Cirilli and Burdese6-8 who showed by X-ray and chemical anal yses that there were two ternary compounds, CaO-Fe0.Fe2O3 and CaO.3FeO-FezO3; the former is the same as that suggested by Schenck et al. and the latter is close to their point X. The results of Cirilli and Burdese show that the phases Y and Z postulated by Schenk et al. are solid solutions of calcium oxide in w?stite. In most of the above-mentioned reduction-equilibria measurements carbon monoxide-carbon dioxide mixtures were used and in a few cases hydrogen-water vapor mixtures were employed. Using the

Jan 1, 1962

By W. D. Robertson, D. A. Koss, A. J. Goldman

THE significance of the hcp (E) structure, which appears when Fe-Cr-Ni alloys (stainless steels) are transformed martensitically, has been the subject of considerable study and speculation.'-7 It has been proposed that the hcp structure is an intermediate phase in the transformation: fcc (austenite) — hcp (E) -bcc (0, martensite). However, recent studies by transmission electron microscopy6,7 have indicated that the hcp structure may be a consequence of the large shear strain (10 deg) associated with the fcc to bcc transformation. That is, the transformation to a bcc structure is accompanied by extensive dissociation of dislocations in the parent austenite, which has a low stacking-fault energy.'-'' X-ray diffraction analysis of the transformed alloy reveals a pattern of lines corresponding to an hcp structure, together with the parent austenite and the bcc product. The fact that the hcp structure is observed only in association with the bcc product in these alloys1'4'6'7 lends support to the conclusion that the hcp structure is a secondary product of the transformation. But, the evidence is circumstantial and more definite resolution of the two possibilities mains to be obtained. If the hcp structure is an intermediate product of the transformation, as in 1) above, then two distinct Ms temperatures should be observed, Ms and To evaluate this possibility, three different techniques that are particularly sensitive to the structural changes accompanying such transformations have been used in an attempt to detect two transformation temperatures in an Fe-15.1 Cr-11.7 Ni alloy: 1) high-sensitivity differential thermal analysis, 2) the temperature dependence of resonant frequency (elastic moduli), and 3) internal friction of cylindrical specimens vibrating in either longitudinal or torsional modes. To obtain the necessary sensitivity, a differential thermal analysis technique was developed for the purpose, Fig. 1. The differential temperature between a nickel standard and the specimen was amplified to produce a sensitivity of 0.02OC (0.7 v) in temperature difference. The specimen and the standard were surrounded by a copper block and the entire assembly was immersed in a solution of methyl and ethyl alcohol, freezing point, - 140OC, which provided the necessary thermal stability to reduce temperature fluctuations to negligible proportions. A cooling rate of about 1.5OC per min was obtained by bubbling liquid nitrogen through the liquid bath. In order to calibrate the experiment with respect to the evolution of heat in the transformation from fcc to hcp structures, differential cooling curves were obtained for an Fe-19.8 Mn alloy, which transforms martensitically to E.'"-' a Ms(e) temperature of 145°C was clearly defined by a temperature

Jan 1, 1964

Q: This is December 1960 and Jafet Lindeberg and myself are sitting around the tape recorder. Jafet, who discovered the gold in Nome, Alaska, in 1898, is going to tell the story of the discovery and of his life up there-a period of some 25 years. Now. Jafet, let's start this off well back of that-start it of1 when you were in Norway and, briefly, tell about when you were born and where you were born, anti so on. Lindeberg: My home in Norway was Varanger in Northern Norway. I was born and raised there and our industry was lumbering, cutting cordwood out of birch, sawing lumber with water power, fishing and dairy work. Q: Did you have anything to do with reindeer? Lindeberg: I never had anything to do with reindeer. But reindeer were raised in the nearby county, called Kautokeino, and they used to come to the coast in the summer, but we had nothing to do with the industry.

Jan 7, 1964

By M. R. Louthan, C. L. Angerman

In polycrystalline Zircaloy-2 the orientation of zirconium hydride precipitates is influenced by an applied stress during hydride precipitation; hydride platelets are oriented nearly parallel to a compres-sive stress and perpendicular to a tensile tress. 1,2 A similar effect has been observed in the Ti-H system, where precipitation of the low-density hydride platelets occurred on habit planes made energetically favorable by the application of stress. 3 Recently, stress activation of hydride habit planes in zirconium and Zircaloy-4 was also demonstrated. The hydrides precipitated on {101l), {112l} and (2131) planes in both zirconium and Zircaloy-4; however, no platelets were found near the prism-plane positions in the Zircaloy-4 samples. Investigations at the Savannah River Laboratory, using polycrystalline Zirc_aloy-2 samples, have confirmed the (101l) and (1121) habit planes but also showed that the prism planes were active hydride habit planes. Using single-surface stereographic analysis and back-reflection Laue techniques, most of the previously reported habit planes for a zirconium were observed.4"1 and one additional plane, the (1013) plane, was noted, Table I. All the habit planes observed had the form (101l) or { 112l) indicating that these planes are the habit planes for hydride precipitation in poly-crystalline Zircaloy-2. The specimens used in these studies were cut from large-grained weld areas of seam-welded tubing and were hydrided in either a static steam autoclave at 400°C and 1500 psig or in a modified Sieverts apparatus at 400°C.

Jan 1, 1967

By H. H. Kaveler, W. R. Evans, Jack Tarner

The geological features, development history and engineering detail of the Shuler Field and the results of approximately two years of unitized operation of the Shuler Jones Sand Pool, were discussed in a prior publication.' The purpose of this paper is to present the results of pressure maintenance in the Shuler Jones Sand Pool after nine years of unit operation. GENERAL INFORMATION The Shuler Jones Sand Pool is located in and about Section 18, Township 18 South, Range 17 West, Union County, Ark. The pool was discovered .in September, 1937, unitized in February, 1941, and subjected to gas injection operations in July, 1941. Water was first returned to the reservoir in July, 1944. The reservoir is an anticlinal trap covering about 4,000 acres. The 154,000 acre-ft of sandstone initially consisted of approximately 150,000 acre-ft of productive oil zone and 4,000 acre-ft of gas-cap. The average depth of production is 7,400 ft. Maximum closure of the reservoir is 135 ft and the oil column lies between a gas-oil contact at -7,270 ft and a water-oil contact at -7,370 to -7,380 ft. The field is approximately four miles long. east and .west, and one and one-half miles wide. The sand grains are angular and vary from fine to medium size. The porosity of the sandstone averages 20.2 per cent. The specific permeability averages 400 md. Some zones have as high as 30 per cent porosity and specific permeability of 4,000 md. The reservoir rock is not uniform in character but consists of sandstone zones interspersed with shale. The variation in rock characteristics is evident in the electric log and core analyses presented in the original publication. Asphalt present in the pore space of the sandstone limited the reservoir to the southeast and apparently blocked any encroachment of water from that direction. The initial reservoir pressure at a subsea depth of 7,300 ft was 3,520 psi. The reservoir temperature was 198ºF. Initially, the solution gas volume was 765 cu ft per bbl and the reservoir volume factor was 1.45. The gas solubility and formation-volume-factors of the reservoir liquid are related with reservoir pressures above 300 psi as follows: Solution gas, cu ft per cu ft, S = 0.0334 P + 18.65 Formation volume factor of reservoir oil, FVF = 8.0 x 10 -5 P + 1.168 Gas volume factor, standard cu ft of gas equivalent to one cu ft of gas at reservoir conditions of temperature and pressure, F = .062 P - 4 Pressure (P) measured in psia. The equation for the gas volume factor presented above is based on a direct measurement of a sample of the gas and is a correction of that used in the original paper. The gravity of the oil produced is from 32 to 34" API. CALCULATION OF INITIAL OIL IN PLACE The Jones Sand production history is interesting because it lends itself to analysis by material balance. Production statistics from discovery of the Jones Sand through 1949 and material balance calculations of the initial stock tank oil in place are shown in Table I. The usual procedure in testing the application of material balance calculations is to compute the apparent initial volume of oil in place, using production and pressure information obtained at different time periods. If the apparent oil in place volumes computed increase with successive time periods, water encroachment is indicated and approximations must be mads to correct for its influence. The first requirement in utilizing such calculations is reliable reservoir pressure, accumulated gas, oil and water production, and PVT data. Calculations of apparent oil in place in the Jones Pool, based on field data

Jan 1, 1951

By W. R. Evans, H. H. Kaveler, Jack Tarner

The geological features, development history and engineering detail of the Shuler Field and the results of approximately two years of unitized operation of the Shuler Jones Sand Pool, were discussed in a prior publication.' The purpose of this paper is to present the results of pressure maintenance in the Shuler Jones Sand Pool after nine years of unit operation. GENERAL INFORMATION The Shuler Jones Sand Pool is located in and about Section 18, Township 18 South, Range 17 West, Union County, Ark. The pool was discovered .in September, 1937, unitized in February, 1941, and subjected to gas injection operations in July, 1941. Water was first returned to the reservoir in July, 1944. The reservoir is an anticlinal trap covering about 4,000 acres. The 154,000 acre-ft of sandstone initially consisted of approximately 150,000 acre-ft of productive oil zone and 4,000 acre-ft of gas-cap. The average depth of production is 7,400 ft. Maximum closure of the reservoir is 135 ft and the oil column lies between a gas-oil contact at -7,270 ft and a water-oil contact at -7,370 to -7,380 ft. The field is approximately four miles long. east and .west, and one and one-half miles wide. The sand grains are angular and vary from fine to medium size. The porosity of the sandstone averages 20.2 per cent. The specific permeability averages 400 md. Some zones have as high as 30 per cent porosity and specific permeability of 4,000 md. The reservoir rock is not uniform in character but consists of sandstone zones interspersed with shale. The variation in rock characteristics is evident in the electric log and core analyses presented in the original publication. Asphalt present in the pore space of the sandstone limited the reservoir to the southeast and apparently blocked any encroachment of water from that direction. The initial reservoir pressure at a subsea depth of 7,300 ft was 3,520 psi. The reservoir temperature was 198ºF. Initially, the solution gas volume was 765 cu ft per bbl and the reservoir volume factor was 1.45. The gas solubility and formation-volume-factors of the reservoir liquid are related with reservoir pressures above 300 psi as follows: Solution gas, cu ft per cu ft, S = 0.0334 P + 18.65 Formation volume factor of reservoir oil, FVF = 8.0 x 10 -5 P + 1.168 Gas volume factor, standard cu ft of gas equivalent to one cu ft of gas at reservoir conditions of temperature and pressure, F = .062 P - 4 Pressure (P) measured in psia. The equation for the gas volume factor presented above is based on a direct measurement of a sample of the gas and is a correction of that used in the original paper. The gravity of the oil produced is from 32 to 34" API. CALCULATION OF INITIAL OIL IN PLACE The Jones Sand production history is interesting because it lends itself to analysis by material balance. Production statistics from discovery of the Jones Sand through 1949 and material balance calculations of the initial stock tank oil in place are shown in Table I. The usual procedure in testing the application of material balance calculations is to compute the apparent initial volume of oil in place, using production and pressure information obtained at different time periods. If the apparent oil in place volumes computed increase with successive time periods, water encroachment is indicated and approximations must be mads to correct for its influence. The first requirement in utilizing such calculations is reliable reservoir pressure, accumulated gas, oil and water production, and PVT data. Calculations of apparent oil in place in the Jones Pool, based on field data

Jan 1, 1951

By R. F. Mehl, C. E. Birchenall

R. E. Hoffman and D. Turnbull—The authors have presented evidence which they have interpreted as indicating that the rate of self diffusion is not intrinsically more rapid at grain boundaries than within the grain. Grain-size effects which apparently exist are attributed rather to impurities concentrated at the grain boundaries. In view of our own experiments and the existing evidence, we believe that the support for this hypothesis is not convincing. We have in progress an investigation in which the rate of self diffusion of silver is being measured over an extended temperature range in both single-crystal and polycrystalline specimens. The results of the single-crystal experiments and some preliminary data on fine-grained polycrystalline specimens have already been reported:' and it is anticipated that a complete report will be published in the near future. The self-diffusion coefficient of large-grained polycrystalline silver (1 grain per sq mm) has previously been measured by Johnson" between 730" and 940°C. The diffusion coefficients which we have measured in single crystals (210 plane normal to diffusion direction) agree within experimental error with values calculated from an extrapolation of Johnson's curve down to temperatures as low as 500 °C. However, it has been demonstrated that the overall self-diffusion rate in fine-grained polycrystalline specimens (initial grain size of 0.003 cm) becomes measurably larger than the overall rate in a single crystal at a temperature of 600°C, and the discrepancy between the two rates becomes greater as the temperature is further decreased. In fact, it has been possible to obtain satisfactory penetration curves for polycrystalline specimens using the sectioning technique at temperatures as low as 400°C. At this temperature, the penetration is 50 to 100 times greater in the polycrystalline specimens than in a single crystal. Fisher" has developed an analysis whereby the ratio of the rate of the unit diffusion process at the grain boundary to the corresponding rate within the grain can be calculated from the penetration curves and an assumption as to the width of a grain boundary. This analysis applied to our data indicates that the unit process at the grain boundary is faster by a factor of 10' at 475°C when the grain boundary width is taken to be 5. The silver used in most of these experiments was obtained from the Handy and Harmon Co. and listed as 99.97 pct pure. Preliminary experiments on 99.999 pct silver from the Jarrel-Asch Co. indicate a grain-size effect of the same order of magnitude as in the less pure silver. Nominally, these purities are as good, at least, as that of the carbonyl iron used by the authors, but of course if an impurity effect does exist its magnitude might be very dependent upon the nature of both major and minor constituents. The authors have cited the work of other investigators who have found no grain-size effects. Neither Steigman, Shockley and Nix" nor Maier and Nelson8 were able to correlate self-diffusion coefficients of copper with grain size. However, all their measurements were performed at or above 750°C; and on the basis of our work with silver, no grain-size effect would be expected at temperatures above about 0.7 of the absolute melting temperature unless the grain size were exceedingly small. Likewise, in the investigation of the self diffusion of lead by Seith and Keil,14 the lowest temperature at which the diffusion coefficient was measured in polycrystalline specimens was 207°C, which is still sufficiently high so that the lack of a grain-size effect is not surprising. Finally, in those experiments on iron from which they concluded that there was no grain size effect, Drs. Birchenall and Mehl seem to have no information as to the actual grain sizes immediately prior to and following the diffusion anneal. Without this information, we believe that their own experiments offer little support for their hypothesis. F. S. Buffington, I. D. Bakalar, and M. Cohen—The results given in this paper agree in order of magnitude with those tentatively reported by us.27 However, significant differences exist in the two sets of data, and it may be well to make an explicit comparison. The diffusion studies at M.I.T. were conducted on somewhat higher purity iron (99.98 pct Fe) than the grades used by the authors, but this is undoubtedly not the answer. Fig. 4 shows the diffusion results of both laboratories for the gamma phase, omitting the authors' data on the commercial steels, while fig. 5 presents a similar comparison for the alpha phase. The divergence is much more marked in the latter case than in the former. In connection with the M.I.T. determinations, all of the runs in the gamma range and those above 800 °C in the alpha range were conducted with specimens having a relatively thick (0.002 cm) electrodeposit of radioactive iron. This practice minimizes any possible error due to extraneous diffusion that may occur during the heating to and cooling from the operating temperature. An exact solution of Fick's law for these boundary conditions was used in calculating the diffusion coefficients. At a later time, three runs were made below 800°C, using very thin electrodeposits similar to those of the authors, and the points fell considerably below the values expected from the extrapolation of the results based on the specimens with the thick deposits (compare dash-dot line in fig. 5). However, in the runs with the thin deposits, deviations of 100 pct were found between the individual specimens, whereas the maximum deviation with the thick deposits was less than 25 pct. Accordingly, it is not known at the moment whether the M.I.T. points below 800 °C should be given as much weight as those above 800°C. If this were done, the frequency factor would be of the order of 400 cm2 per sec, which is quite high. In other metals, the frequency factor for self diffusion lies between about 0.1 and 10 cm2 per sec. As the points below

Jan 1, 1951

By Alfred H. Bell

Drilling activity increased in Illinois in 1935. There were 34 com-pletions as compared with 26 in 1934 and 18 wells were drilling at the end of 1935. Some large blocks of acreage were leased in Marion and Clay counties near the central part of the Illinois structural basin. Production of oil in the state totaled 4,305,000 bbl., a decrease of 4 per cent from that of 1934 There was some curtailment of production in the early part of 1935 but none after April 30 as shown in the following table. Percentage Pro-duced of Potential ProductioN (USING September 1934 Period as BaSis) Jan. .l-Feb. 20............................................ 79 Feb. 21-Feb. 25............................................ 85 Feb. 26-Feb. 38............................................ 79 Mar. 1-Mar. 11............................................ 85 Mar. 12-Mar. 31............................................ 100 Apr. 1-Apr. 9.......................................... 80 Apr. 10-Apr. 30............................................ 86 May 1-Dec. 31........................................... 100 This is equivalent to an average curtailment throughout the year of 5 per cent. The price of Illinois crude oil at the wells remained constant during 1935 at $1.13 per barrel. A small amount of oil was sold at a 1ower price, notably from the Dupo field, but to arrive at a value for the state's production there would be little error in assuming an average price of 81.13, giving a total value of $4,864,465. The following table shows production in Illinois by moths in 1935, according to the U.S. Bureau of Mines. Jan............. 332,000 May.......... 382,000 Sept ,............. 370,000 Feb............. 295,000 June. ........... 858,000 Oct.............. 391,000 Mar............ 370,000 July............ 377,000 Nov............. 369,000 April............ 338,000 Aug............. 379,000 Dec............ 344,000

Jan 1, 1936

By Alfred H. Bell

Drilling activity increased in Illinois in 1935. There were 34 com-pletions as compared with 26 in 1934 and 18 wells were drilling at the end of 1935. Some large blocks of acreage were leased in Marion and Clay counties near the central part of the Illinois structural basin. Production of oil in the state totaled 4,305,000 bbl., a decrease of 4 per cent from that of 1934 There was some curtailment of production in the early part of 1935 but none after April 30 as shown in the following table. Percentage Pro-duced of Potential ProductioN (USING September 1934 Period as BaSis) Jan. .l-Feb. 20............................................ 79 Feb. 21-Feb. 25............................................ 85 Feb. 26-Feb. 38............................................ 79 Mar. 1-Mar. 11............................................ 85 Mar. 12-Mar. 31............................................ 100 Apr. 1-Apr. 9.......................................... 80 Apr. 10-Apr. 30............................................ 86 May 1-Dec. 31........................................... 100 This is equivalent to an average curtailment throughout the year of 5 per cent. The price of Illinois crude oil at the wells remained constant during 1935 at $1.13 per barrel. A small amount of oil was sold at a 1ower price, notably from the Dupo field, but to arrive at a value for the state's production there would be little error in assuming an average price of 81.13, giving a total value of $4,864,465. The following table shows production in Illinois by moths in 1935, according to the U.S. Bureau of Mines. Jan............. 332,000 May.......... 382,000 Sept ,............. 370,000 Feb............. 295,000 June. ........... 858,000 Oct.............. 391,000 Mar............ 370,000 July............ 377,000 Nov............. 369,000 April............ 338,000 Aug............. 379,000 Dec............ 344,000

Jan 1, 1936

By Donald L. Katz

The equilibrium constants developed by Souders, Selheimer and Brown1' have been very useful tools in predicting vapor-liquid equilibria during the past five years. Their equilibrium constants were computed by assuming ideal solutions and recognizing the deviations of vapors from ideal gas laws. The same fundamental concepts were used by Lewis and co-workers8 for predicting vaporization phenomena by means of fugacities. The equilibrium constant is defined by equation 1: y\x =K [1] in which K = equilibrium constant, y = mol fraction of a constituent in the vapor phase, x = mol fraction of the constituent in the equilibrium liquid phase. The equilibrium constants are a function of temperature and pressure and might be considered as replacing the ratio of the vapor pressure to the total pressure of Raoult's law. They may be used to compute the vapor or saturation pressure of a liquid or the dew point of a vapor for any pressure or temperature from the analysis of the mixture much as Raoult's law is used. Likewise, the quantity of a mixture that will vaporize at any equilibrium temperature and pressure and the composition of the vapor and liquid may be calculated. The purpose of this paper is to review the available equilibrium data of interest in petroleum production, to discuss the auxiliary physical properties of the hydrocarbons, and to present typical uses of the equilibrium constants. The particular applications chosen are the computation of the results of stage separation of crude oil and natural gas, the calcula: tion of a pressure-volume curve of a crude oil-natural gas mixture, and information gleaned from a consideration of reservoir equilibria.

Jan 1, 1938