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By H. A. Schwartz

From time to time, one of the authors has had occasion to investigate the graphitizing reaction and has published the results mainly as discussion' of the work of other investigators. In view, therefore, of the diversity of both observations and interpretation, it seemed well to attempt, a revision of the entire subject in the Research Laboratory of the National Malleable Castings Co. The work consisted of a careful study of a single, impure, iron-carbon alloy. The material, which may be considered typical low-carbon white cast iron of the malleable industry, was an air-furnace iron of the following composit,ion: carbon 2.30 per cent., silicon 1.20 per cent., manganese 0.29 per cent., phosphorus 0.156 per cent., sulfur 0.048 per cent. The freezing range extended from 1213' to 1132' C., the latter figure agreeing with Gontermann's data.2 We have attempted to define the equilibrium diagram of this alloy, in the stable condition as related to the mctastable diagr,aui,- from a temperature somewhat below the euteetic freezing point to a temperature l>clow Arl and for a graphitic-carbon content from practically notliing to the original total rarbon of the specimen (see Fig. 6). More csp~c~ially we desired to locate the line in the stable diagra~n corrcspo~idi~lg to thc Ac, line of the metastable syst,ern, which is designated by analogy, thc At, line (t, from tcrnpcr carbon); also to dctermirle the locat'ion of A tm witah respect, to Acm t,o~vard their lowcr extremities at Arl in ordei to determine whether or not graphitization is completed by th~ separation of an iron-carbon entectoid analogous to pearlite in the iron-cementite system. This would involvc furthcr a colnparison of thc locations of Ihc stablc and met.astable 41 points. As the carbon concelltrations of thc solid solutions of the two syste~~ls are probably not, identical, an explanation of t>lieir differences and of thc,

Jan 1, 1923

By D. D. Smith, D. P. Squier, E. L. Dougherty

A system of differential equations describing the temperature behavior of fluid injected at constant surface temperature in a well is derived and .solved analytically. A formula for the fluid temperature at any time and depth is given, as well us a special formula valid for very large times. These formulas are used to calculate temperatures for several typical cases. The results indicate that, initially, the temperature of the water entering the formation is considerably lower than the injection temperature. This condition lasts for only a short period— less than three days for most cases of practical interest. Following this highly transient period, during which the temperature of the fluid entering the formation builds up to about 50 to 75 per cent of the injection temperature. the system enters a quasi-steady state in which the temperature changes are very slow. After severl years, the bottom-hole temperature will still be 50" to 100°F lower than the injection temperature, hilt the heat losses may he tolerable. INTRODUCTION Predicting the behavior of a hot-water flood requires that the temperature of the water entering the injection interval be estimated. This report describes the development and solution of a system of equations which describes the temperature behavior of the injected water in the wellbore with certain simplifying assumptions. The only previous means known to the authors for describing such a process is that of Moss and White.' Their results appear to be close to those obtained by our method in the practical cases which were compared; this agreement is largely due to the fact that in our method temperature soon approaches a quasi-steady state, as was assumed in their method throughout. However, our model covers all times, is continuous (whereas the Moss-White model depends on breaking the depth into discrete intervals) and. we feel. more closely describes the physical problem. FORMULATION OF THE PROBLEM PHYSICAL SYSTEM AND ASSUMPTIONS The injection procedure consists of pumping water at a fixed surface temperature T., down an infinitely long cylindrical well or tubing of inner radius Any material exterior to the water column such as mud, casing, or cement is regarded as part of the formation. The general behavior of the system may be described qualitatively as follows. When the hot water is first introduced into the system, the temperature difference between the formation and the water is large, resulting in a high rate of heat transfer. As a result, the temperature adjacent to the wellbore rises very quickly. Because the segment of the formation adjacent to the wellbore largely controls the heat transfer rate, the heat transfer rate will become relatively constant when this portion has reached a temperature close to that of the water opposite it. The temperature of the water and formation then increase very slowly with time. The length of the initial highly transient period and the temperature of the water at its conclusion will be functions of depth, injection rate, injection-string radius, surface injection temperature and the physical properties associated with the water-formation system. The following additional assumptions were made. 1. There is no heat transfer by radiation in the system. 2. There is no heat transfer by conduction in the vertical direction in either the injection stream or the formation. 3. The linear volumetric and mass flow rate of the water is constant throughout the injection stream. 4. No horizontal temperature gradient exists in the injection stream. 5. The product of density and heat capacity is constant for both the water and the formation, and the formation thermal conductivity is constant. 6. Initially, both the water in the wellbore and the reservoir are at a temperature given by the (constant) ambient surface temperature plus the product of depth and geothermal gradient (assumed constant). At large distances for the wellbore (r m), the formation will remain at this temperature. 7. The water temperature and the formation temperature at r — r,, are equal for all depths D. DERIVATION OF EQUATIONS The differential equation satisfied by the fluid temperature T,(D, t), which is obtained by writing a heat balance on a cylindrical differential of volume dV of the injection string between the depths D and D i dD, is

By F. H. Froes, D. H. Warrington

Electron microscope evidence which indicates that TaC may precipitate at random sites in the matrix is presented. Initially the particles are almost spherical and coherent with the matrix. However, as they grow in conditions in which there are insufficient vacancies to relieve lattice strain, the particles rapidly lose coherency in two directions and continue to grow as plates with approximately the full lattice mismatch strain present perpendicular to the plane of the plate. The necessary relief of strain comes from dislocations loops which do not become visible until the later stages of aging. The rapid decrease of apparent strain to low values of appoximately 1 pct at small particle sizes arises not from a complete incoherency but from applying a model wrong for the particle shape and strain distribution. PREVIOUS work has shown that MC-type carbides may precipitate intragranularly in austenitic stainless steel on dislocations,1&apos;2 in association with stacking faults,3&apos;4 and randomly through the matrix,5-7 In investigations of the matrix precipitate by thin-foil electron microscopy, considerable lattice strain has been found to occur around the precipitating phase.7&apos;8 Attempts have been made to evaluate the amount of lattice strain by using the methods developed by Ashby and brown.9,10 Values of the linear strain, much less than the 17 pct theoretical mismatch (for TaC), have been reported; it has been suggested that this is due to either a loss of coherency1&apos; or vacancy absorption which occurs during either the initial nucleation or growth of the precipitate." This report is an extension of earlier work7 that dealt with the precipitation of TaC from an 18Cr/12Ni/ 2Ta/O.lC alloy after it had been quenched from 1300°C and aged between 600" and 840°C. In particular, the shape of the precipitate particles and the amount of strain in the matrix, due to the precipitate, have been studied. The work described here is part of a wider investigation of factors that affect carbide precipitation in austenitic stainless steel," details of which are to appear elsewhere. RESULTS The present investigation can be conveniently split into two aspects of the strain-fields surrounding the matrix particles: 1) information derived from the strain-field which indicates the shape and habit plane of the precipitate particles and 2) the magnitude and sign of the strain-field. The Shape and Habit Plane of the TaC Precipitate. In the early stages of aging twin lobes (normally black F. H. FROES, formerly at the University of Sheffield, Sheffield, England, is Staff Scientist, Colt Industries, Crucible Materials Research Center, Pittsburgh, Pa. D. H. WARRINGTON is Lecturer, Department of Metallurgy, University of Sheffield. Manuscript submitted November 1, 1968. IMD on white background, i.e., for the deviation parameter, S > 0) that indicate the strained region of the matrix define the position of the particles by bright field transmission electron microscopy. The actual particles were not detected until they were approximately 120Å diam; below this size they were too small to be imaged in the electron microscope. This meant that particle growth that had occurred before this stage had to be inferred from the matrix strain-field contrast. In all cases when diffraction effects were observed from the precipitate particles, a cube-cube orientation relationship (i.e., (llO)ppt Il<llO>matrix and {1ll }ppt {III} matrix) existed between the precipitate and the matrix. From the matrix precipitate particles lying along edge-on {111} planes (e.g., at A, Fig. I), the precipitates are seen to be plate-like with their diameter being roughly 18 times their thickness after 5000 hr at 650°C. However, the exact shape of the particles cannot be determined because of the masking effect of the strain-field contrast. If a dark-field micrograph, using a precipitate reflection, is studied, Fig. 2, a number of the projected images of the TaC particles [on the (110) foil surface] apear to have straight edges parallel to projected f111) planes. Thus, it appears that in the later stages of aging the TaC particles are plate-like with some tendency for the edges of the plate to be bounded by the matrix close-packed {ill} planes (though the general shape of the particles in the plane of the plate is circular and thus the "diameter" of the particles has a real physical significance). It should be noted that the bands of fine discrete particles observed in Figs. 1 and 2 are not the matrix precipitate discussed in this paper but are precipitates associated with extrinsic stacking faults3j4 occurring on (111) matrix planes. **£** ****** \ *x 23 Fig. 1—18/12/2~a/0.1~ alloy. Solution treated at 1300°C for 1 hr, water quenched, and aged 5000 hr at 650°C. The (112) directions shown are the traces of the e&e-on (111) planes. Foil normal [110]; operating reflection (331); bright field micrograph.

Jan 1, 1970

By Ling Yang, John Henderson

Self-diffusion coefficients of copper in molten copper have been measured by the capillary reservoir method in the temperature range 1140o to 1260°C. The results can be represented by the equation D = [(1.46 * 0.01) x 10-3) exp [(-9710 * 710)/RT] cm2/sec. The energy of activation agrees within the limit of experimental uncertainty with that for viscous flow. The relationship between the diffusivity and coefficient of viscosity is best described by the equation D = kT/4pnr cm2/sec. MEASUREMENT was made of the self-diffusion coefficient of copper in molten copper in the temperature range 1413º to 1533ºK, using the capillary reservoir technique and CU64 as the radioactive tracer.The procedures for filling the capillaries, making the diffusion run and evaluating Dcu from the counting results were the same as described previously.1,2 All experimental operations involving the melt were carried out in a purified argon atmosphere. A graphite crucible, enclosed in a McDanel tube, was used as a container for the melt because of its satisfactory nature as a refractory material and the low solubility of carbon in copper. Graphite was also used for the capillary material. A McDanel thermocouple sheath, to which graphite radiation shields were affixed, was used to hold the capillaries. By moving this sheath through a rubber seal at the top of the McDanel tube, the capillaries could be lowered into or raised out of the melt. A Globar furnace with a constant temperature zone (± 2°C) of 2 in. was used to heat the assembly. The temperature of the furnace was the equilibrium value corresponding to a given setting of the transformer. Temperature was measured with a Pt-10 pct Rh/Pt thermocouple and varied during a run

Jan 1, 1962

By L. A. Roe, John Jan

Iodine is a soft, lustrous, grayish-black nonmetallic element with a density of 4.9. It is the least active of the four members of the halogen family. The other members are, in order of increasing activity, bromine, chlorine, and fluorine. Iodine is a solid at ordinary temperatures, while bromine is a liquid and chlorine and fluorine are gases. Iodine melts at 113°C and volatilizes at 184.4°C to a blue-violet gas with an irritating odor. It occurs in nature only as iodates and iodides or other combined forms. It was discovered by Bernard Courtois in France in 1811, who noticed its presence as an unknown substance in crude soda ash obtained from burning seaweed. Gay-Lussac recognized it as a new element and named it iode, from the Greek word "ioeides or iodes" for violet color (MacMillan, 1970). The world production is not known with any great certainty, but it is probably between 25 and 35 million lb per year, of which about 30% is consumed in the United States. Geology and Mineralogy Iodine compounds occur as a minor constituent as a mineral in the Chilean nitrate deposits and in solution in brines and seawater. According to the US Geological Survey, it is the 47th most abundant element in the earth&apos;s crust. The minerals lautarite, Ca (I03)3 (calcium iodate), and dietzeite, Cat (103)2 (CrO4), (calcium iodate-chromate) are found in Chilean nitrate deposits which are located in Antofagasta and Tarapaca provinces on the eastern slope of the coast range in a desert area. Various brines contain iodine compounds. Seawater contains about 0.05 ppm of iodine and some seaweeds will extract and accumulate it up to 0.45% on a dry basis. Some coals in West Germany also contain iodine compounds. The known and potential sources of iodine reported in 1968 are given in Table 1. Table 2 lists estimated world iodine reserves. Iodine has been recovered from brines in Java, Indonesia, France, England, and the USSR. Iodine has also been recovered from seaweed in Ireland, Scotland, France, Japan, Norway, and the USSR. The indicated reserves and future resources of iodine are large but have never been adequately measured. Analysis Iodine as the free element can be detected by the characteristic blue color it gives to a starch solution. Quantitatively it is determined as the free element by titration with standard thiosulfate solutions using starch as an indicator. Colorimetric methods are also applicable. Markets and Prices Iodine and its compounds are generally marketed in the form of: iodine, crude; iodine, resublimed; calcium iodates; calcium iodide; potassium iodide, sodium iodide, and numerous organic compounds. Product Specifications Crude iodine, World market: 99-99.5% 12. Crude iodine, US produced, average: 99.8% 12. Crude iodine, USP XVII Specs: not less than 99.8% percent I2. Resublimed iodine is usually 99.9% and ACS specifications call for not over 0.005% total bromine and 0.020% nonvolatile materials (Anon., 1971). Prices, c.i.f. United States, for iodine have been steadily increasing from $1.18 per lb of crude in 1967 to $6.37-7.27 in January 1981 (Anon., 1981). In 1980 the price of iodine increased by 50%.

Jan 1, 1983

By J. R. Lucas, R. L. Frantz

Mine sealing programs for the alleviation of acid mine drainage were begun by the Federal Government in the &apos;30&apos;s. As part of an acid mine research project to The Ohio State University, a field test was undertaken to determine the effectiveness of mine seals for reducing mine acid. Details of the tests made at the McDaniels mine show the feasibility of air-sealing and flooding an acid-producing drift coal mine. Work by the University continues. The Federal Government undertook in the early thirties an extensive mine sealing program for the alleviation of acid mine drainage. In the states of West Virginia, Ohio, and Pennsylvania many general summaries have been made on this program but no critical evaluation with supporting data has been found on the effectiveness of mine seals for reducing mine acid. Because of this it was decided to undertake a field testing program as part of an acid mine research project of the Engineering Experiment Station, The Ohio State University. The objective of this phase of the project was to develop and install a field research laboratory for acid mine drainage studies. Specifications for such a mine laboratory were developed and resulted from the following considerations: 1) Size and preservation—the test mine shou1d be of limited size to permit frequent and detailed examinations; it should be in a reasonably sound condition to permit safe entry. 2) Isolation—the mine should be physically separated from all other mines. 3) Openings—a minimum number would be desirable to reduce the sealing problem. 4) Structure—the mine especially near the openings should be structurally sound. 5) Acid production—the mine should be producing significant quantities of acid. After considerable searching, the McDaniels mine was selected in the Hocking coal field in Vinton County just above Lake Hope State Park in southeastern Ohio. The small drift mine in the middle Kittaning coal consisted of two small rooms with one mine opening about 6 ft above a seasonal stream bed. Before it was finally decided to seal the mine, a short study was made of the acid drainage over several months. Fig. 1 shows a plot of acidity (milligrams per liter), flow (gallons per minute), and acid production (pounds per day) vs time over the sampling period. Because the coal was overlain with a porous sandstone, the mine drainage was consistent the year around even though the mine was

Jan 1, 1961

By William A. Longacre

In a previous paper the author discussed the problem described by the title of this paper, outlining and reviewing the Gish-Rooney method, with comparison and brief analysis of the interpretation techniques of Roman2 and Tagg.3 Some aspects of the simple type of two-layer system were reviewed from various sources.4, 5, 6 The Two-layer Problem For the configuration shown in Fig. I, and for any electrode separation A, the SurfAce of earth p, DepthH i P2 Infinite depth Fig. i.—Two-Layer system. apparent resistivity is a function of the relative depth the overburden resistivity pl, and a factor K defined by the equation P2 + P1 where p, is the resistivity of the lower bed. Thus, by the known theory of electrical images, p = pi [1+ */(*-7)] where The Multilayer Problem As the number of isotropic, homogeneous, horizontal layers increases, the difficulties of interpretation multiply. The theory becomes much more involved, and in view of the state of our knowledge, the general problem is virtually impossible of exact solution. However, certain types of multilayer problems can be worked out in terms of two-layer theory. Humme1,7 Pirson,8 Tagg,3 Watson,9 and others have pointed out the possibility of building up approximations of multilayer resistivity curves with suitable combinations of two-layer curves. Many three-layer curves can be constructed in this way to a good degree of accuracy, and special types of four-layer curves can be approximated. It is very likely that as the number of layers increases, the method of combination will not give good approximations except in very special cases. In the analysis of actual field data, the author has found that many obviously multilayer curves can be solved partially with a good degree of accuracy, using the theory that thin adjacent beds may be considered as one layer or zone, and applying two-layer theory to the extremities of the field curve. Modified Tagg Method of Interpretation Tagg&apos;s second method, though superior to his first, necessitates a large number

Jan 1, 1946

By William A. Longacre

In a previous paper the author discussed the problem described by the title of this paper, outlining and reviewing the Gish-Rooney method, with comparison and brief analysis of the interpretation techniques of Roman2 and Tagg.3 Some aspects of the simple type of two-layer system were reviewed from various sources.4, 5, 6 The Two-layer Problem For the configuration shown in Fig. I, and for any electrode separation A, the SurfAce of earth p, DepthH i P2 Infinite depth Fig. i.—Two-Layer system. apparent resistivity is a function of the relative depth the overburden resistivity pl, and a factor K defined by the equation P2 + P1 where p, is the resistivity of the lower bed. Thus, by the known theory of electrical images, p = pi [1+ */(*-7)] where The Multilayer Problem As the number of isotropic, homogeneous, horizontal layers increases, the difficulties of interpretation multiply. The theory becomes much more involved, and in view of the state of our knowledge, the general problem is virtually impossible of exact solution. However, certain types of multilayer problems can be worked out in terms of two-layer theory. Humme1,7 Pirson,8 Tagg,3 Watson,9 and others have pointed out the possibility of building up approximations of multilayer resistivity curves with suitable combinations of two-layer curves. Many three-layer curves can be constructed in this way to a good degree of accuracy, and special types of four-layer curves can be approximated. It is very likely that as the number of layers increases, the method of combination will not give good approximations except in very special cases. In the analysis of actual field data, the author has found that many obviously multilayer curves can be solved partially with a good degree of accuracy, using the theory that thin adjacent beds may be considered as one layer or zone, and applying two-layer theory to the extremities of the field curve. Modified Tagg Method of Interpretation Tagg&apos;s second method, though superior to his first, necessitates a large number

Jan 1, 1946

By Randall L. Neal

This paper discusses the impact of taxes at the state and federal level on typical on-shore oil and gas exploration economics in the USA. Taxes considered are the windfall profits excise tax, state production (or severance) taxes, state income tax, and federal income tax. Also considered will be market prices for oil and gas in the USA. The effect of government take as a percent of revenue, on rate of return, discounted Payout, and discounted cumulative cash flow is shown on the attached tables. The conclusion drawn is that tax laws, while rarely the most important factor to be considered when drilling a well, can have significant impact on the profitability of oil and gas ventures, and should be considered when determining where to drill. Hypothetical exploration wells were analyzed for the impact of tax laws on project profitability. The results of this study show that when factors other than taxes are postulated to be the same (such as producing rate, capital, operating costs, and prices), cash flow can vary by as much as 68% due to the differences in the tax laws. Other significant findings for the cases studied include: (a) that discounted payout varied by as much as 1.8 years, (b) that rate of return differed by up to 67% and (c) the total tax rate as a percentage of revenue had a maximum variance of 33%.

Jan 1, 1982

Jan 1, 1965

By E. A. Almond

An attempt is made to explain the effect of stress on strain aging by examining the mechanism of yielding for a group of aged dislocations. The experimental results on which the theory is based indicate that a linear relationship develops between the aging stress and the discontinuous yield effect in a low carbon steel THE discontinuous yield effect that occurs in bcc metals after strain aging is usually explained by the interaction of interstitial atoms with individual dislocations. Attempts have been made to interpret the kinetics of strain aging in terms of interstitial segregation to nonrandom groups of dislocations1-3 but apart from Li&apos;s4 work little or no effort has been made to examine the effect of groups of aged dislocations on mechanical properties. It appears likely that such groups can be stabilized if a positive load is maintained on the specimen during aging5 and, furthermore, that the enhanced strain aging effect associated with aging under load might be due to the stability of these aged groups. The effects associated with this latter phenomenon have been described by Almond and Hull, Ref. 5, Figs. 2 and 3, and it is found that the upper yield stress, the lower yield stress, and the yield point elongation are increased by aging under load. The yield point elongation reaches a maximum value but the enhanced effect persists in the upper and lower yield stress values even after extended aging treatments when the general level of the flow stress curve rises. The flow stress, as measured at 8.5 pct total strain, however, is independent of aging stress. Almond and Hull5 showed that it was unlikely that the differences in mechanical properties could be caused by stress enhanced diffusion and they suggested that the effect was in some way associated with the different dislocation distributions that are obtained when specimens are aged with and without an applied stress. At that time no explanation was offered for the strengthening effect produced by stabilized dislocation distributions but additional tests have been performed to establish a quantitative relationship between aging stress and mechanical properties, and also to examine more closely the effect of varying the procedure for applying the aging stress. EXPERIMENTAL The material used was an iron wire containing 0.015 wt pct C, 0.002 wt pct N, and 0.006 wt pct 0. Tensile specimens with a 1 cm gage length and 0.08 cm diam were annealed at 850°C for 1 hr in vacuum to establish a grain diameter of 0.032 mm and then aged at 200°C for 24 hr. After this treatment the amount of carbon left in solution would be less than 10-4 wt pct, and ni- as aging time is increased. It is suggested that this observation, and effects that arise from varying the method of applying the aging stress, can be explained by a strengthening mechanism whereby dislocations are more difficult to move when they are aged in piled-up groups. trogen would be the main cause of strain aging. Tensile tests were performed in a hard beam machine at a constant crosshead speed of 0.02 cm per min and the specimen chamber was immersed in a temperature controlled silicone oil bath at 32" * 0.05"C. RESULTS All specimens were prestrained 5 pct before aging under stress and the results in Figs. 1 to 5 show the effect of aging time and aging stress on the following parameters ?UY = auy — ?F(5); i.e., the difference between the upper yield stress after aging,?uy, and the flow stress after prestraining 5 pct, ?f(5). ?LY = sly —sf(5); the difference between the lower yield stress after aging, ojy, and the flow stress after prestraining 5 pct. s8.5 = the flow stress at 8.5 pct total strain after aging at 5 pct strain. Varying the Loading Procedure. Three variations in the procedure for applying the aging stress were examined; i) After prestraining, the specimen was unloaded to a stress of 18 kg mm-2, aged at that stress, and then tested. ii) After prestraining, the specimen was unloaded to 2 kg mm-" then reloaded to 18 kg mm-&apos;, aged at that stress, and tested. iii) After prestraining, the specimen was unloaded to 18 kg mm-&apos;, aged at that stress, then unloaded to 2 kg mm- before testing. Specimens were unloaded or reloaded by decoupling a clutch in the drive transmission of the tensile machine. This enabled the crosshead to be driven manu-

Jan 1, 1970

By Enrique Hauser

Discussion of the paper of ENRIQUE HAUSER, presented at the New York meeting, February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 521 to 534. GEORGE A. BURRELL, Pittsburgh, Pa. Mr. Hauser determined the influence of inert gases on the properties of fire-damp mixtures, and one might take some issue with his work on the effect of hydrogen, on those mixtures. It is valuable information to have, but as far as the practical application of it goes, it is not of much significance, because one does not find it in mines, at least not in any appreciable amount. The same Fig. 1.-APPARATUS FUR DETECTING COMBUSTIBLE GASES IN AIR. thing can be said of ethylene. Ethylene is formed in considerable quantities as a product of heat reaction, but normally, in the coal mines, as a result of a great many analyses we have made at the Bureau of Mines, we cannot say that ethylene is a combustible gas found in the fire-damp in coal mines.

Jan 5, 1916

By Hiram B. Woon

Uranium ore deposits in the Lisbon Valley area are in an arcuate belt, 15 miles long by one-half-mile wide, on the southwest flank of the Lisbon Valley anticline. They range in size from 500 to 1,500,000 tons and by mid-1965 had yielded 6,147,000 tons containing 48,530,000 pounds of U3O8. Ore bodies average 6 feet thick, are tabular, amoeba-shaped masses, concordant to the bedding, and are in the thickest, lowest sandstone unit of the Moss Back Member of the Chinle Formation of Triassic age. The host rock is predominantly a fluviatile, calcareous, fine-grained to conglomeratic sandstone. Uraninite, the principal ore mineral, fills the pores in the sandstone and partly replaces sand grains and fossil wood fragments. During Late Permian and Early Triassic time pre-Chinle Formations were arched to form the ancestral Permian anticline. Moss Back streams truncated Moenkopi and Cutler beds which capped the ancestral anticline and then covered it with fluviatile elastics, which were subsequently covered by thousands of feet of Triassic, Jurassic, and Cretaceous sediments. Uranium, probably derived from the Chinle Formation by diagenetic processes, was transported in connate ground waters, was moved by compaction or hydrostatic forces, and was deposited under reducing conditions. Uranium was emplaced around the crest of the ancestral anticline, prior to the Laramide orogeny. During the orogeny, the Tertiary-Lisbon valley anticline was super induced on the Permian anticline and, penecontemporaneous with uplift, was faulted parallel to its longitudinal axis. The Big Indian ore belt on the southwest flank footwall block was elevated to approximately its present position, and the northeast flank hanging wall block was elevated only slightly. An extension of the Big Indian ore belt around the northeast flank of the ancestral Permian anticline may exist in the Moss Back sandstone in the downthrown block northeast of the Lisbon Valley fault.

Jan 1, 1968

By K. O. Stamm, B. A. Rogers

Because it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,l which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has devel oped recently concerning the reversibility of the transformation. From thermo-dynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912" for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9I8° and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rater of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°C. and concluded that a change occurs reversibly between 907&apos; 3" and 910" 3°C., probably between 907" and 910°C. Wells, Ackley, and Meh16 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, ½°, and .?°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909. 5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien eiements were low enough, the A3 transformation would be completely reversible at 909.50 + 1°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1942

By B. A. Rogers, K. O. Stamm

Because it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,l which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has devel oped recently concerning the reversibility of the transformation. From thermo-dynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912" for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9I8° and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rater of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°C. and concluded that a change occurs reversibly between 907&apos; 3" and 910" 3°C., probably between 907" and 910°C. Wells, Ackley, and Meh16 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, ½°, and .?°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909. 5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien eiements were low enough, the A3 transformation would be completely reversible at 909.50 + 1°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1942

By V. Koump, T. F. Perzak, R. H. Tien

A series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts Mere measured during essentially one-dimensional freezing of Al-Cu alloys. The dimensions of the ingots were 3 by 5 by 6 in. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experitments. For each alloy the rate of heat removal was varied to give a total jreezing time in the range 3 to 30 min. The results of these measurements cowlpared favorably with the theoretical model of freezing of binary alloys with time-dependent surface temperature. IN engineering analysis of solidification of commercia1 steels and nonferrous alloys it is a common practice to assume that an alloy freezes by propagation of an isothermal solidification front, i.e., essentially as a pure metal. In two recent theoretical investigations&apos;j2 the present authors explored the possibility of a more realistic approach to the problem of solidification of alloys. In the proposed model the freezing of an alloy is assumed to take place by propagation of two isothermal fronts, i.e., the liquidus front and the solidus (or eutectic) front. The region between the two fronts contains both liquid and solid and is referred to as the solid-liquid region. The width and the solid content of the solid-liquid region vary with alloy type, solute concentration, and cooling rate. For a given alloy system, initial concentration of solute, and the mode of heat removal, the proposed model yields the temperature distribution within the solid skin, temperature, solid fraction, and concentration distributions with the solid-liquid region, and the rates of propagation of the liquidus and the solidus fronts. This model is obviously of considerable practical importance in engineering analysis of solidification processes, since it gives a more realistic estimate of skin strength during solidification and a better estimate of the total freezing time. Before the new model can be used with confidence, however, it is necessary to test this model experimentally. The experimental testing of the proposed model is a relatively simple matter since the effects to be measured are large and a relatively simple experiment will suffice. The theoretical model predicts, for example, that during freezing of an alloy containing substitutional type solute (negligible diffusion in the solid during freezing) the solid-liquid region occupies an appreciable portion of the ingot, even at low concentration of solute.&apos; Another prediction of the theo- V. KOUMP, formerly with U. S. Steel Corp., is now with Research and Development Center, Systems and Process Division, Westinghouse Electric Corp., Pittsburgh, Pa. R. H. TlEN is Senior Scientist, Fundamental Research Laboratory, U. S. Steel Corp., Research Center, Monroe ville, Pa. T. F. PERZAK, formerly with U.S. Steel Corp., is now with Fiber Industries, Greenville, S. C. Manuscript submitted March 6, 1968. IMD retical model, easily verifiable by experiment, is that the rate of propagation of the solidus (or eutectic) front increases as the solidus front approaches the center of the slab. This prediction is contrary to well-known behavior of the solidification front during freezing of pure metals, where the rate of propagation of the solidification front decreases with time and freezing is completed at the lowest rate. A rather severe test of the proposed model is provided by comparison of theoretical predictions and experimental measurements of the effects of cooling rate and composition on the rates of propagation of the liquidus and the eutectic fronts. In order to test the soundness of the formulation and the method of solution of the problem of solidification of alloys a series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts were measured during essentially one-dimensional solidification of A1-Cu alloys. The A1-Cu system was chosen strictly as a matter of convenience. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experiments. For each alloy the rate of heat removal was varied to give the total freezing time in the range 3 to 30 min. The results of these measurements are compared with the predictions of the theoretical model of solidification of binary alloys, with time-dependent surface temperature.&apos; Before the experiments described in this paper were undertaken, a serious attempt was made to utilize the measurements of previous investigators to test the theoretical model. In the course of this preliminary study a careful review was made of experiments of Pellini and coworkers3 and Doherty and Melf~rd.~ The measurements in Pellini&apos;s work were carried out using a steel containing at least four major components. Evaluation of the solid fraction-temperature relation for this steel (required in the theoretical model) is difficult and uncertain. Doherty and Melford, on the other hand, measured the solid fraction-temperature relation experimentally, but did not give sufficient data to explore the effects of composition and the cooling rates on solidification. Hence it was not possible to utilize these measurements to test our theoretical model. EXPERIMENTAL METHOD The experimental technique used in this investigation differs somewhat from the more conventional techniques employed in solidification studies. This technique was developed primarily to eliminate con-vective mixing in the molten metal caused by pouring of molten metal into the mold. In our experiments A1-Cu alloys were melted directly in the mold. The mold assembly used in solidification experiments is shown in Fig. 1. The mold was fabricated from *-in. stainless-steel sheet. The dimensions of

Jan 1, 1969

By Otto H. Henry, Edward L. Badwick

Up to the present time, according to Hansen1 and Haughton,2 the constitution of the bismuth-indium system has not yet been published. The generally accepted value for the melting point of indium, as listed in most scientific journals and textbooks, is 155°C. Recently, however, H. M. Davis3 has determined a new melting point for indium of 257.3°C ± 0.1°C. Since bismuth has been used in preponderance as an alloying element in the majority of low-melting alloys, and indium has been used with considerable success in lowering the melting points of low-melting alloys,4,5 an interest has been developed in the application of these two metals, making a complete knowledge of the constitution of its alloys desirable. In this investigation, the melting point of indium reported by H. M. Davis has been found to be substantially correct. A value of 157.2°C ± 0.5°C was determined. The two eutectic compositions have been placed at 34 and 50 pct bismuth with their respective eutectic temperatures as 72.4&apos;C ± 0.5°C and 90°C ± 0.5°C. The bismuth-indium phase diagram has been determined by thermal and microscopic analysis and is shown in Fig I. THERMAL ANALYSIS Granulated bismuth and indium shot, having a guaranteed purity of 99.99 and 99.95 pct, respectively, were melted in a carbon crucible by means of a laboratory heater. To minimize oxidation of the alloys, a heavy mineral oil (Nujol) having a high flash point was used. A platinum-platinum rhodium thermocouple 0f fine wire encased in a thin-walled Pyrex glass tube, about 1/8 in. in diameter, was connected to a type K potentiometer for temperature measurements. The thermo-couple was calibrated against the melting points of tin, bismuth, and the silver-copper eutectic and the boiling point of water. Since the temperature readings could be reproduced to 0.2°C, and the accuracy of the temperature standards in this range is slightly better than 0.5°C, it seems reasonable to assume that the temperature readings are reliable to approximately 0.5°C. The cooling rate could be controlled by varying the amount of insulation surrounding the crucible. Three or four layers of asbestos paper, 1/16r, in. thick, sufficed to give a cooling rate of from 1° to 2°C per minute. Undercooling was slightly noticeable. This condition was minimized by vigorous stirring, since the advantage of using slower rates was too small to justify the greater expenditure

Jan 1, 1947

BECAUSE you cannot always proceed by the ordinary pathway since you sometimes find yourself in a place where you cannot have all that you might need or wish, it often happens that it is necessary to know how to recognize and understand your materials well, in addition to having them well disposed, and to know how to use your, ingenuity in arranging a mould., Furthermore, things have a great diversity among themselves, and it is not possible to give a particular rule for all. But if you have a certain broad fundamental knowledge when you have need of many things, the ingenuity awakens and supplies its needs by imitation. Now, because I have thought that you had not hitherto had the slightest shadow of knowledge of what I have described in this treatise of mine, I have expanded and narrated things in greater detail than perhaps I might have done. For this reason I have also decided that I wish to tell you of several methods that can be used if you wish to mould, especially in making an intaglio* for a relief, t or in making another intaglio in bronze from either an intaglio or a relief. And I will tell how every relief reduces, itself from convex to concave and also how the relief is made from the intaglio. These works are first made of plaster or pastes or some other liquid thing that is soft when moulded and becomes hard either by drying out with heat or by shrinking with cold, such as tragacanth, plaster of Paris, sulphur, lead, wax, or similar things. And, in conclusion, we describe the method of making an intaglio from a solid. In making an intaglio you must first consider whether it is a large or small thing, figure or foliage, whether it is in demi- or bas-relief, and whether it is a thing that projects from the mould wholly or in part.

Jan 1, 1942

By J. A. Cahill, A. D. Kirshenbaum

Using an alumina or zirconia crucible with an alumina sinker or a molybdenum sinker coated with zirconium dioxide, the density of liquid iron was determined by the immersed-sinker method over the temperature range of 1800" to 2500°K. The density, with respect to temperature, is ex-Dressed by the equation Dg/cm = 8.523 - 8.358 X 10 T&apos;K The molar Volumes and thermal coefficients of expansion were calculated. Iron, upon me1ting, was found to expand 3.5 pct. A basic knowledge of the physical properties of materials at high temperatures is becoming increasingly important. A check of the literature shows, that in spite of the importance of iron, very few measurements have been made of its physical properties in the liquid state. Density measurements have been made by Benedicks and his collaborators1g using the method of balanced columns, by Desch and smith4 using the immersed sinker method with an alumina sinker, by Lucas using the maximum bubble method5 and by Stott and endall&apos; who used an alumina pyknometer. In the method of balanced columns, the difference in level of molten iron in two arms of a U-tube, together with the corresponding difference of pressure had to be measured. The formation of gas bubbles in one or both arms was a great source of error. These values are very erratic. They vary from 6.83 to 7.45 g per cm3 at the melting point (1805"~) and from 6.45 to 7.15 g per cm3 at 1890°K. Stott and Rendall determined the density at 1837"K, with a reproducibility of *0.2 pct. They used an alumina pyknometer fired to 1973°K. The vessel was filled in a vacuum furnace by immersion in the liquid metal. When thermal equilibrium was attained, the pyknometer was withdrawn, cooled, the ingot removed and then weighed. The chief disadvantage of the method was the difficulty of inserting the pyknometer without cracking it. The authors have been able to determine the density of liquid iron from its melting point up to 2500°K, by using the immersed-sinker method, with A1203 or ZrOz crucibles and A1203 or molybdenum sinkers coated with Zr02, Fig. 1. EXPERIMENTAL Apparatus. In these studies the source of heat was the carbon tube resistance furnace with an argon atmosphere described previously.7 Experimental runs were made using either Ala3 or ZrOz crucibles. The sinkers used were 1) pure A1a3 and 2) molybdenum coated with ZrOz. The crucible, 2 1/8 in. in diam and 3 in. high, was centered in the furnace on an Ala3 of Zr02 pedestal. The sinker, 1/2 in. in diam and 1 1/2 in. long, together with a counter weight, was suspended from an analytical balance into the melt by a molybdenum wire. Procedure. The procedure, as described previously,&apos; consisted in measuring the weight loss of the sinker in the liquid iron while determining simultaneously the liquid iron temperature by means

Jan 1, 1962

By Horace R. Graham

CHEMICAL nitrogen and the "nitrates" of commercial significance are derived mainly from three basic sources: (1) the natural deposits in the form of nitrate-bearing earth and clay, which, being largely water-soluble, can exist only in the most arid portions of the earth; (2) coal, which yields not only nitrogen but also the additional by-product hydrogen required for the synthesis of ammonia and its compounds; (3) the atmospheric air, which contains 75.5 pct by weight of pure nitrogen gas. NATURAL NITRATE DEPOSITS Occurrence Although natural nitrate deposits consisting principally of the salts of sodium and potassium have been reported in Egypt, South Africa, Mexico, Argentina, Colombia, Peru and the USA, the only known natural nitrate resources of commercial importance are the vast deposits found in the Atacama, Tarapaca and Antofagasta regions of northern Chile, lying in a narrow strip 10 to 50 miles wide and roughly 450 miles long, between latitudes [19O] and [26OS]. In addition to yielding nitrates of sodium and potassium, these deposits are the source of the major portion of the world&apos;s supply of iodine. The nitrate-bearing ores known in Chile as caliche are variable in composition and may contain from 5 to 30 pct each of nitrate, chloride and sulphate. While the deposits are present chiefly in the form of the sodium salt, potassium, magnesium and calcium also occur in percent- ages from 0.1 to 5; usually as double salts with sulphate, which are but slightly soluble in nitrate leach solutions. These double salts are bloedite(Na2S04.MgS04.4H,0), glauberite (Na2S04.CaS04), polyhalite (K2SO4.- MgS04.2CaS04.2H20). Some deposits contain up to30 pct of their ni-

Jan 1, 1949