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By W. Randolph Van Lewis

In determilling the relative rate and in fi~lding the point where different inlpurities containecl in copper-matte are eliminated during the process of a converter-blow, the follo~ving results were obtainecl : A converter was selected which was starting on its sccolld charge. The first charge after lining had finished its copper " hot," and conseqaently no copper was adhering to the sides of the lining. All the copper and granulated slag from the previous charpc mcrc dumped, thus removing ally possibility of " salting " the matte to be tested. The coliverter worked fast and well during the entire test. Periods of ten minutes were selected. The converter mas brought from the stack to secure each sanlple of matte to be

Jan 1, 1904

By W. C. Phalen

E. G. SPILSBURY; New York, N. Y.-I would like to emphasize what Mr. Phalen says in his paper regarding the possible utilization of the waste acids in the West for the acid concentration of phosphate rock, and to call attention to the fact that this is already being done by Mr. Laist at Anaconda, who is producing concentrated phosphoric acid from these low-grade rocks. During the last year, he has not been able to carry this along to the extent he, had expected, owing to the tremendous demand which they have had for all the acid they can produce, so instead of having a. surplus of acid, as was expected, they are really short of this material for their electrolytic copper and zinc work.

Jan 4, 1917

By Joseph Mac Donald

Stripped of its romantic possibilities, mining is a commercial business, carried on for the profit there is in it; and the business of the manager, in its ultimate analysis, is to make the profit as large as possible. The general manager of a mining company should keep himself personally familiar with all the details of its operations. If he fails to do so, chaos results, labor becomes inefficient, costs go up, and profits go down. Nowhere is this emphasized more than in Mexico. If the mining operations are extensive and complex, involving, besides the work of mining the ore, its transportation and treatment by various milling operations, and the marketing of the products, the business, to be carried on properly, must be

Jan 1, 1909

By C. H. Reynolds, Robert C. Pruess

Late in 1954 exploratory drilling indicated a substantial orebody on the Rattlesnake claims of Woodmont Inc., a Continental Uranium Inc. subsidiary. Woodmont holdings are located about 35 miles southeast of Moab, Utah. Only a few miles north of Big Indian Valley and other Chinle-sand uraninite deposits, the claims are in an entirely different geologic environment. Detailed development drilling continued until the Deep North orebody was outlined, covering an area approximately 300 x 450 ft. All exploratory drilling and about 80 pct of development drilling was wet core. Chemical assays for each hole sample, applied at 1-ft intervals against the measured core length, were put into a conventional ore calculation formula. Forty-six holes were drilled to delineate the Deep North orebody.

Jun 1, 1956

I have attended these meetings, every year, since 1926 and have served on both the Pittsburgh and the National Executive Committees, so that I am fully aware - of the ruling of this organization regarding, "No Papers by Vendors". Since I am now classified as a VENDOR, I wish to express my sincere appreciation for the invitation to formally discuss these very interesting papers --all of which herald the coming of an entirely new era in the manufacture of quality steels. I also appreciate the references by Mr. Mosser and Dr. Swinkels to my first paper on the oxygen probe which was presented at the meeting of this group, here in Chicago, in 1966 and was subsequently published in the NOH Proceedings of that year. (1)

Jan 1, 1972

By W. A. Oates, J. A. Lambert, P. T. GaIIagher

Monte Carlo methods have been used to compute the arrangements of interstitial atoms dissolved in tetrahedral sites in bcc lattices. It is assumed that the presence of an interstitial atom "blocks " a certain number of neighboring sites and prevents their occupancy. Sites "blocked" by more than one filled site are allowed for. The computed values of. the mean occupation number (defined as the ratio of the total number of sites blocked to the number of solute atoms are used to calculate the configurational entropies of the solutions. These entropies are compared with those resulting from previous theoretical studies of this problem and also with available experin~ental data for the p Zr-H, Nb-H, V-H, and Ta-H systems. Evidence is also given that the "blocking" explanation of low limiting compositions in these systems, rather than this being due to initial limitations on the number of sites available, is probably correct. THE ideal partial configurational entropy of mixing of an interstitial solute in a metal is given by: where p is the number of interstitial sites per metal atom and Xi is the atomic fraction of the interstitial. For the bcc lattice. which we shall be concerned with in this paper, the interstitial positions are shown in Fig. 1. It can be seen that for the tetrahedral sites, p=6. whereas for the octahedral sites, p = 3. Different emphasis has been placed on the relative importance of energy and entropy effects in determining deviations from ideality in interstitial solid solutions. In some cases the same system, e.g., Fe-C, has been described by the contradictory regular and athermal solution models indicating that the enthalpy and entropy functions, derived from equilibrium data, are frequently not accu.rate enough to differentiate between these treatments. However, for certain metal-hydrogen solutions the equilibrium data is available over sufficiently wide ranges of temperature and composition to permit a reasonably accurate determination of the compositional variation of the heats and entropies. Hoch&apos; has attempted to interpret the results of interstitial solid solutions in terms of a regular solution model. In the case of the Ta-H system where 13 = 6, this model entails fitting the experimental relative partial entropies of solution, asH, to the equation: where ASgs is the relative partial excess entropy of solution of hydrogen. Hoch found that the results of Mallett and Koeh1 could be fitted to this equation with an approximately constant value of AF up to XH = 0.25. However, it is apparent from the solubility isotherms in this system which become asymptotic to the composition TaH that, since (Xh /6 - ~Xh ) becomes infinite only at TaH6, it is necessary that AS<&apos; tends to infinity at TaH. In other words, the low saturation composition of TaH, instead of the anticipated TaH,, eliminates the possibility of applying regular solution theory to such systems. Rather large negative excess configurational entropies must exist at higher hydrogen concentrations in order to explain the lower saturation values. To account for these low limiting compositions and excess entropies two distinctly different approaches have been followed. Rees and many others1-l2 have assumed that not all interstitial sites are crystallographically equivalent with respect to the interstitial addition; that is, in Eq. [I] p is less than the value anticipated from geometrical considerations. To describe, say, a bcc metal-hydrogen system with a limiting composition of MH by this approach one would consider that p = 1 in the first instance instead of p = 6.&apos;j3 In some cases, nonintegral values of B have been taken in order to improve the fit with the experimental data over limited ranges of composition. The other approach which has been used to explain the low saturation compositions is to assume that, although all sites are available for occupancy, strong repulsive interactions exist between the neighboring interstitial atoms, and hence occupancy of any site excludes or blocks a certain number of neighboring sites from being occupied. Earliest treatments of this concept considered the exclusion of an integral number, of nearest-neighbor sites from being occupied at all concentrations. In this case, the partial configurational entropy is given by: These early treatments failed to allow for the overlap of the blocked sites which will arise at all but the very lowest concentrations. More recently attempts have been made to calculate the effect of this decrease in the number of blocked sites on the configurational entropy. Using the quasichemical treatment of interstitial solid solutions as given by Lacher and assuming that an infinite repulsive interaction energy existed between the solute atoms. atom obtained an approximate configurational entropy applicable to the blocking with overlap case:

Jan 1, 1970

By F. Wald, A. J. Rosenberg

The general features of the constitution of the B-Pt system were determined using standard rnetal-lograph~c, thermoanalytic, and X-ray diffraction techniques. Three compound were found. Two of these, Pt3B and Pt,B, are formed by peritectic reactions at 523° and 890°C, respectively. The third, Pt3B,, is congruently melting with a flat maximum at 940°C but decomposes eutectoidally in to Pt,B ant1 boron nt - 600° to 650°C. THE low-temperature allomorph of boron (red, simple rhombohedra1 a boron) is of scientific and technological interest as an elemental semiconductor.&apos; However, the studies of this material have been hampered by its reported instability above 1200"~ which precludes crystal growth from the melt (mp - 2200°C). Crystallization from platinum solutions has been suggested as an alternative crystal-growth technique, but has met with only limited success.&apos; The technique depends upon the existence of a significant difference between the eutectic temperature and the transformation temperature of boron. In order to clarify the conditions for further crystal-growth experiments, we found it desirable to redetermine the main features of the B-Pt phase diagram since previous reports on the system1&apos;5&apos;6&apos;7 are in marked disagreement. EXPERIMENTAL The experimental methods used were thermal analysis, metallography, X-ray analysis, and, to a lesser extent, measurements of microhardness. Most of the alloys were prepared from spectrograph-ically standardized boron obtained from Johnson-Matthey &Co., Ltd. (212 ppm impurities, exclusive of carbon and oxygen) and platinum powder obtained from F. Bishop & Co. (200 ppm impurities, mainly of other platinum group metals). Some alloys were also prepared with very high-purity, float-zone refined boron (99.9999 pct obtained from "Wacker Chemie" and extrahigh-purity platinum (99.999 pct) obtained from Johnson-Matthey & Co., Ltd. The reported results did not depend on the choices of these starting materials. Five-gram alloy specimens containing 10, 20, 25, 27.5, 30, 33.3, 34, 35, 37, 37.5, 38, 39, 40, 41, 42, 43, 45, 50, 55, 60, 70, and 80 at. pct B were made by melting the elements together in boron nitride crucibles using rf heating of a graphite susceptor, either in vacuum or under high-purity argon. All alloys were heated to at least 1800°C for -5 to 15 min. Most of the alloys did not wet the crucibles when the latter were outgassed by preheating under vacuum. In any event, no weight loss was detected after melting, and the nominal composition was assumed for all specimens. Thermal analysis on 2.5-g samples were carried out in boron-nitride crucibles under a vacuum of 5 x X torr. The apparatus was heated in a "Kan-thal A 1" wound furnace, which limited the maximum temperature to about 1100°C. The output of the indicator thermocouple was fed to a dc recorder with a 1-mv full-scale span and an adjustable zero. The apparatus was calibrated repeatedly, using the freezing points of high-purity aluminum, silver, and gold. The results justified the use of the NBS voltage vs temperature tables for Pt/Pt 10 pct Rh thermocouples. All thermal analyses were run at least twice and both the heating and cooling effects were recorded. Most of the alloys had a very strong tendency to supercool. However, the use of mechanical vibration permitted reproducibility within *5°C for all alloys, except in the region around 40 at. pct B. Only the cooling effects are plotted in Fig. 2, since they appear to be more reliable. For metallography, the alloys were cut with a diamond cutting wheel, cast in a polymethacrylate resin, ground and polished with diamond paste, and etched with dilute aqua regia, a common etch for platinum alloys. Both copper and molybdenum radiation were employed to obtain X-ray diffraction data using Debye-Scherrer cameras and a "Norelco" diffractometer Diffractometry with high scanning speeds (1 deg per min) using nickel filtered CuK, radiation was used to identify the main regions of the diagram. However, molybdenum radiation was used for the detection of boron, since the latter showed very strong absorption and fluorescence effects with CuK, radiation. RESULTS AND DISCUSSION Three intermediate compounds, corresponding to the compositions Pt3B, Pt2B, and Pt3B2, were found in the system. Fig. 1 reproduces their X-ray diffraction spectra, together with those of pure boron and pure platinum. As can be seen from the thermal-analysis data in Fig. 2, Pt3B and Pt2B are formed by

Jan 1, 1965

By M. J. Marcinkowski, A. S. Sastri

A detailed compressive stress-strain analysis and transmission electron microscopy investigation has been made of the deformation behavior occurring in a 50 at. pct Ni-Ti (hypoeutectoid) alloy and a 54.5 at. pct Ni-Ti (hypereutectoid) alloy. In the case of the hypoeutectoid alloy, three stages of work hardening are observed. Stage I occurs at a very low stress and is associated with plastic deformation via martensite formation. Stage 11 is characterized by very rapid work hardening and is due to difficulties in causing further deformation in the fine martensite aggregate produced in Stage I. Stage III which occurs at very high stress levels is characterized by smaller work hardening rates and is due to the plastic deformation arising from alternate reconversions of the original martensites to martensites of varying orientation. Rapid quenching of the hypereutectoid alloy leads to very high yield strengths and is related to a fine precipitate dispersion that such treatment brings about. The present investigation represents the final phase of a three-part study directed toward an understanding of the solid-state transformations in near equi-atomic Ni-Ti alloys as well as the deformation mechanisms associated with these alloys. In the first part,"2 to be henceforth referred to as I, it was found that alternate simple shears on {112} planes and in (111) directions convert the parent B2 structure in the equiatomic NiTi alloy into two distinct close-packed monoclinic martensites. All of the marten-sites were of this type, whether they were formed by cooling or by plastic deformation, whether induced to form in bulk samples or in thin foils, or whether examined in the electron microscope at room temperature or below. On the other hand, in the second part of this investigation,3 to be reffered to as 11, it was shown that upon slow cooling to about 640°C. alloys in the neighborhood of NiTi which possess the B2 structure transform eutectoidally into their equilibrium phases Ti2Ni and TiNi3. However, preceding the formation of these equilibrium phases a series of metastable intermediate phases are formed. This paper will set as its goal the elucidation of the remarkable deformation behavior exhibited by NiTi. In particular, Buehler and Wiley4 have found equiatomic NiTi to be surprisingly soft, while Buehler et al.5 have shown this alloy to possess a memory effect: i.e., upon bending at room temperature it will revert to its original shape when heated to above about 50°C. In I it was shown that NiTi was soft in the sense that the yield stress was low; nevertheless, the alloy work-hardened at an extremely rapid rate to very high stress levels. On the other hand, the hypereutectoid alloys with somewhat higher nickel, say 54.5 at. pct (60 wt pct) have enormously increased yield strengths compared to those of the equiatomic alloys. In order to determine the atomistic processes giving rise to the above behavior, it was decided to examine samples that were wafered from bulk specimens deformed in compression to various strains using the techniques of transmission electron microscopy. EXPERIMENTAL TECHNIQUE All of the alloys used in the present investigation contained either 50 at. pct Ni (55.06 wt pct) or 54.5 at. pct Ni (60 wt pct) and were arc-melted in the form of a finger using the same techniques described in I and II. The finger was capsulated in a stainless-steel jacket and swaged at 850°C into rods. Compression specimens 0.300 in, long and 0.200 in. in diam were machined from these rods. In order to completely re-crystallize the samples and remove residual stresses, all of them were capsulated in evacuated quartz, annealed for 1/2 at 1050°C. and then furnace-cooled. Compression tests were carried out in an Instron tensile testing machine covering a range of temperatures from —196° to 200°C using procedures described previously.6&apos;7 In all cases crosshead speed was 0.02 in. per min. Wafers 0.015 in. thick were spark-cut from the cylindrical samples at 45 deg to the compression axes after they had been deformed to the desired strain. These specimens were then spark-planed to about 0.005 in. and then electrochemically thinned for examination by transmission electron microscopy as described in I.

Jan 1, 1969

By R. W. Stormont, F. Wald

The phase diagram of the Pseudobinary section PbTe-Fe was determined. It was found to contain a monotectic and a eutectic reaction, the latter one taking place at 14 at. pct Fe and 875° * 5°C. The solid solubility of iron in PbTe was found to be 0.3 at. pct by electronmicroProbe analysis. No solubility of PbTe was detected in iron. Slight deviations from true pseudobinary behavior were found to occur in the range of - 5 to 10 at. pct Fe. In the course of a general investigation of reactions of various metals with lead and tin telluride,&apos; the lead telluride-iron system was reinvestigated. It had been established much earlier than iron does not chemically react with lead telluride but forms a eutectic with a melting point of 879" The eutectic composition or other related information has never been reported, but for a number of years iron has been in general use for contacting of lead telluride and lead telluride alloys for thermoelectric applications. It seems therefore desirable to clarify the exact constitution of the system to furnish a base for the long-term evaluation of bonds made between lead telluride and iron either by pressure contacting or by brazing methods. I) EXPERIMENTAL METHODS Lead telluride-iron alloys were prepared in 10-g charges, using premelted lead telluride. This material was prepared from high-purity, semiconductor-grade lead and tellurium obtained from the American Smelting and Refining Co. and described as 99.999 pct pure. The iron used was "Armco" iron; the major impurities found here were 0.02 pct C, 0.018 pct Si, and 0.015 pct Cr. All remaining impurities were less than 0.01, the total of all impurities not exceeding 0.15 pct. Charges were prepared in closed quartz arnpoules which were evacuated and in some cases backfilled with high-purity argon to retard excessive lead telluride evaporation and deposition in slightly cooler parts of the ampoule. For high iron concentrations, this can lead to total separation of the constituents, since the vapor pressure and the sublimation rate of PbTe are quite high.4 Nevertheless, since the ampoules are closed, no change in overall composition was expected and the nominal composition of all alloys was assumed to be retained. X-ray diffraction analysis, thermal analysis, and microsections were used in the evaluation of the alloys. The nature of the system was such that X-ray diffraction was not particularly helpful. It merely served to establish that at all concentrations PbTe and a! iron were in equilibrium at room temperature. Thermal analysis was carried out by taking direct temperature vs time curves on a Sargent recorder where a width of 10 in. was kept as 1 or 0.5 mv by use of an automatic bucking voltage network. Quartz ampoules with minimized dead space, coated with boron nitride and fitted with a thermocouple reentrant, were used as containers for the charge. At high temperatures and over long periods of time, boron nitride reacts with iron. For the thermal analysis runs, however, this was not significant. More significant was the fact that the vapor pressure of PbTe at some of the meas -uring temperatures apparently exceeded I atrn quite considerably. This, in some cases, caused the slightly softened quartz tubes to blow out if great care was not taken to contain them and minimize time and temperatures used. As containers pure nickel tubes were used which also served to avoid temperature gradients in the quartz ampoule. Nevertheless, the experimental difficulties at high temperatures were severe and the monotectic temperature could therefore not be determined accurately. In general, the accuracy reached by the thermal analysis setup in this case is *4"C as determined with gold, silver, and tin, under the conditions of analysis here. Inherently, the apparatus is capable of reaching accuracies better than i 1°C. Also, difficulties were encountered in microsection-ing. They were related to polishing, since it is rather difficult to avoid pulling the iron out of the weak and brittle lead telluride matrix. It proved best to follow a procedure where, after grinding to 600 grit on carborundum paper, a polish with 6 p diamond was used on nylon cloth. Finally, #3 "Buehler" alumina and an automatic polisher were used for -5 min only, to avoid relief. The best etching results were achieved with

Jan 1, 1969

By W. Rostoker, R. F. Domagala, R. P. Elliott

The phase equilibria of the Hg-Th system over the composition range 0-100 pct Th and temperatures up to 1000°C have been studied for a small-volume, closed system. The solubility of Th in liquid Hg is about 5 pct at 300°C and decreases sharply with decreasing temperature. Two intermediate phases occur, Hg3 Th and HgTh. The structures of these are hexagonal (nonideally close-packed) and face-centered cubic, respectively. The HgTh phase decomposes eutectoidally at 400°-500°C. The solubility of Hg in solid thorium seems to be negligible. AFULL-phase diagram for this system would have to be defined on temperature-composition-pressure co-ordinates. This paper describes the pseudo phase diagram of a closed system, that is, where the alloy enclosed in a small volume equilibrates with a vapor pressure of mercury dictated by composition and temperature. Because of the experimental difficulties in studying a system of this nature, many of the phase relations can only be sketched. Alloy Preparation Alloys over the full range of composition were made from triple distilled mercury and one of two grades of thorium. For the bulk of the work, a calcium-reduced metal in sintered pellet form of reported 99+ pct total thorium content was used. Arc-melted specimens of this thorium gave a hardness of 135 VPN. The microstructure showed small primary dendrites of ThO2. A number of alloy compositions were made with a high-purity, iodide-decomposition thorium metal. The are-melted hardness of a button of this material was 35 VPN. Although the microstructure of the arc-melted specimens showed no dendrites of ThO2, there was definite evidence of an unidentified phase enveloping the grain bound-aries. There were no distinguishable differences between the constitution of alloys made with the two grades of thorium metal. Under normal conditions thorium is not wetted by liquid mercury. The film of ThO2 on all thorium metal cannot be penetrated by either liquid or vaporous mercury. It was therefore necessary to comminute thorium in the presence of mercury under such conditions that oxide films could not reform on the newly exposed metal surfaces. This was accomplished by the use of a high-speed, carbide-tipped rotary cutter incorporated in a chamber purged with argon and connected at the bottom to a demountable Vycor bulb containing a weighed amount of mercury. This experimental device is fully described in a separate paper.1 Alloy compositions were calculated by weighing the empty bulb, the bulb containing the mercury, and the bulb containing the mercury and the thorium chips. Many alloys were analyzed chemically for thorium and/or mercury after subsequent homogenization; the agreement between analyzed and calculated compositions was invariably very close. Bulbs containing the requisite amounts of mercury and fine thorium chips were clamped off, removed to a sealing unit, evacuated and sealed. Amalgamation under these conditions proceeded rapidly even at room temperature. To insure homogeneity, the specimens were annealed to 300-400°C. Alloys containing less than 30 pct Th remained pasty after all treatments, indicating an equilibrium condition of liquid plus solid. Alloys with more than 30 pct Th were transformed into a dark powdery product. These latter specimens were annealed for times of up to 1 week to complete interdiffusion. Many of the alloy compositions are pyrophoric. On exposure to air they oxidize with considerable evolution of heat to a mixture of ThO2 and free mercury. It was mandatory that alloy specimens be handled in a "dry box" purged thoroughly with argon. All X-ray diffraction specimens were powdered, screened, and sealed in capillary tubes within the dry box. Experimental Procedures Thermal analysis experiments, useful only in the mercury-rich region of the system, were conducted with the alloys in their original containers. A reentrant thermocouple well formed an integral part of the bulb. These bulbs were heated in a silicone oil bath and cooled in a dry ice-acetone mixture. The rates of heating and cooling were slowed by immersing the specimen bulb in a larger tube containing silicone oil. This provided a suitable thermal lag. In all tests, pure mercury was run as a basic standard. While the invariant reaction at about the melting point of mercury was detected by thermal analysis, the heat effect at the liquidus was not sufficient to produce an inflection in the cooling curve. It was necessary to determine the liquidus temperatures at the mercury-rich end of the system by "breaks" in electrical reslstivity versus temperature curves for individual alloys. The apparatus for this purpose consisted of a pyrex tube about 2 in. diam and 12 in

Jan 1, 1959

By T. A. Read, M. S. Wechsler, D. S. Lieberman

A theoretical analysis of the austenite-martensite transformation is presented which predicts the habit plane, orientation relationships, and macroscopic distortions from a knowledge only of the crystal structures of the initial and final phases. THIS paper presents a new theory of the formation of martensite. This theory makes possible the calculation of the austenite planes on which the martensite plates form, the orientation relationship between the austenite and martensite crystal axes, and the macroscopic distortions which are observed. The only input data needed are the crystal structures and lattice parameters of the austenite and martensite. Considerable effort has been devoted over the past thirty years to the development of an understanding of the crystallographic features of martensite reactions. Much of this work has been done on steels and iron-nickel alloys, for which a great deal of data has been accumulated concerning the shape and orientation of the martensite plates, the relative orientations of the austenite and martensite crystal axes, and the observable distortions which result from transformation. These observations are reviewed in refs. 1, 2, and 3. The first major step toward an understanding of these phenomena was made in 1924 by Bain,&apos; who showed that the a body-centered cubic structure can be produced from the 7 face-centered cubic structure by a contraction of about 17 pct in the direction of one of the austenite cube axes and an expansion of 12 pct in all directions perpendicular to it. Since that time, most of the efforts at further interpretation have been made by investigators who have worked from the phenomenological data, incorporating some of the information from the lattice properties, and have sought an analysis into likely deformations which would produce the observed results."- "11 but the three most recent papers on the subject have already been reviewed in some detail." Machlin and Cohenl0 measured the components of the distortion matrix and verified that the habit plane is a plane of zero distortion and rotation for the (259) case. They showed that the measured distortion matrix, when applied to the parent lattice, does not yield the product lattice and hence some inhomogeneous distortion must occur. Frank,u working from the lattice properties and taking some clues from the observations, considered the correspondence of close-packed rows and planes in the austenite and martensite. He predicted substantially the observed lattice relationship and habit plane for certain steels which have a (225) habit. Geisler12 suggested that there is a natural tendency for the habit plane to be a (111) and postulated certain slip processes to account for the fact that the experimentally observed habit plane is irrational and deviates from the assumed one. The present work differs from previous treatments of martensite formation in that it permits calculation of all the major manifestations of the process. Habit plane indices, orientation relationships, and observable distortions are all calculated from a knowledge of the crystal structures of the initial and final phases alone. The calculations contain no adjustable parameters. The agreement found between calculated results and the observations reported in the literature constitutes powerful evidence in favor of the mechanism of martensite formation proposed. The theory is applicable to systems other than steel (as is discussed later in this paper) which exhibit a diffusionless phase change but because of the wide-spread interest in the austenite-martensite transformation, particular attention will be given to the iron-base alloys. For other systems which undergo a similar face-centered cubic to face-centered tetragonal transformation, the mathematical treatment is identical with that presented here. Hence the theory successfully describes the transformation in the indium-thallium alloy.&apos;" Homogeneous Transformation to Martensite The distortion which any homogeneously transforming volume of austenite undergoes in order to become martensite is shown in Fig. 1, as was first suggested by Bain.&apos; (This distortion will hereafter be referred to as the "Bain distortion.") This specification of a contraction along one cube axis ;ombined with an expansion in all directions perpendicular to this axis describes what is properly called the "pure" distortion associated with this transformation. The distinction between a "pure" and an "impure" distortion plays an important part in the discussion which follows. A "pure" distortion is characterized by the existence of at least one set of orthogonal axes fixed in the body which are not rotated by the distortion. (These are called the "principal axes" of the distortion.) No such set of axes exists in the case of an "impure" distortion. On the other hand, an impure distortion can always be represented as the result of a pure distortion combined with the rotation of the specimen as a rigid body. For a given impure distortion the corresponding pure distortion

Jan 1, 1954

By S. S. Arentz

PLANNED health and safety programs have become an essential part of American industry because such programs lead to increased operating efficiency, improved labor relations, better public relations, and to substantial savings in compensation insurance. Those of you who have had the unpleasant duty of informing the wife or widow of one of your men of his serious injury or death while on the job, know that all the benefits of a successful safety program do not show on the balance S. S. ARENTZ, Member AIME, is General Superintendent, Nevada Operations, Combined Metals Reduction Co., Pioche, Nevada. AIME San Francisco Meeting, February 1949. TP 2741 A. Discussion of this paper (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Jan. 6, 1949. sheet. These programs are of particular importance to the mining ,industry because mining&apos;s reputation as an unusually hazardous industry and the commonly isolated location of mining operations tend to focus attention on these problems. Description of Operations: Before proceeding with a discussion of our health and safety programs at Pioche, it may be proper to give a brief description of Pioche and of our operations there. Pioche is one of the early Nevada mining camps. It was founded shortly after the discovery of high grade silver ore in 1863 and mining has continued with more or less regularity to the present day. In an era of lawlessness, Pioche was notorious. The story persists that 75 men died with their boots on before one died a natural death, and old payroll records show that nearly as many gunmen were employed to stand off claim jumpers as there were miners working the mine. That was probably as close to a safety program as the times permitted. Pioche is situated in southeastern Nevada on the main highway between Ely and Las Vegas. The camp is on the flank of "Treasure Hill," near the original silver discovery, at an elevation of about 6000 ft. The present day population of about 2000 is primarily dependent upon the mines of the area, although Pioche also serves as the county seat of Lincoln Couqty and as the center of the surrounding livestock industry. The camp is served by a branch of the Union Pacific Railroad and receives power from the generators at Hoover Dam. The Pioche operations of the Combined Metals Reduction Co. were started in 1923 when the first complex lead-zinc ore was shipped to the company&apos;s mill at Bauer, Utah. The modern mill at Pioche was completed in 1941. The operations are medium sized in the nonferrous field, employing an average of 350 men in the mine, mill, and related works. The complex lead-zinc ore is mined from replacement deposits in a comparatively flat, extensively faulted, limestone horizon. Mining methods vary from stull-supported open stopes to filled square-set stopes. The thin bedded limestone and shale overlying the ore is allowed to cave as areas are mined out and caving frequently follows closely upon ore extraction. The relatively heavy ground and the numerous faults add to the problems of safe mining. The mine is well mechanized and the mill and surface plant are modern and well equipped. Labor is organized in a C.I.O. union and labor-management relations have been unusually harmonious. During most of the period since 1923 a competent supervisory staff worked to reduce safety hazards but the primary responsibility for safety rested on the individual workman. Accidents happened and all too frequently they were regarded by all concerned as unavoidable. In October 1939, the late Robert L. Dean became superintendent at Pioche. Most of his previous experience had been in the fields of iron and coal mining and from that experience he brought the concept that no accident is unavoidable. Many of the features of our present health and safety programs were initiated by Mr. Dean during his term as superintendent. Health Program: Our health program centers in Dr. Q. E. Fortier and his new, well-equipped, and well-staffed, modern hospital in Pioche. The program starts with a thorough pre-employment physical examination and is followed by yearly re-examinations at the expense of the company. The Pioche Mutual Benefit Association, to which all Pioche mine operators and employees belong, pays benefits covering hospitalization and surgery expense incurred by employee members and their families. The Association is governed by a board of directors elected by its members. The mine operators of the district donated the original capital and pay the monthly dues of the employee members. The employees pay the dues covering members of their families. Though not strictly a part of the

Jan 1, 1951

By D. W. Loucks

There is plenty of evidence to indi-cate that at least one of man&apos;s chief interests in life is to make himself as comfortable as possible. If you doubt this, just watch the fellow next to you for the next half hour trying to find the most comfortable position that a hard chair has to offer. Comfort, however, does not always mean an easy chair. To some, it may mean a wealth of money; to another, freedom from worry. But to most of us, it means first of all a comfortable atmosphere in which to live, and to a great many of us it probably also means freedom from that annoying task of firing the furnace. Today more than ever before. automatic heat is one improvement that is placed high on everyone&apos;s list. Perhaps this is because automatic heating is becoming relatively cheaper. Perhaps it is because of a good publicity campaign on the part of the oil and gas men or maybe it is just that we are getting lazier day by day. At any rate, almost every issue of Better Homes and Gardens, House Beautiful, or your other favorite home magazine carries an article extolling the virtues of this or that automatic heating system. If I were to ask you to name the first thing that came to your mind when I said automatic heat, you would prob-ably say either gas furnace or oil burner. Or if you had just been studying heating systems, you might possibly say heat pump. But chances are you would not mention anything about coal, and yet coal is the most common source of the greatest automatic heat of them all. I say this because coal is the fuel used almost universally by the district heating industry in producing and delivering to certain heavily populated areas heat ready to use at the touch of a valve or the click of a thermostat. Although the industry is over a half century old, it has not experienced the widespread development of other utility industries because of certain limitations which I believe you will realize from the next few minutes discussion. District Heating Operations We may define district heating as any operation where two or more buildings are heated from a central heating plant. The method of heat transfer may be hot water or in some cases warm air, but generally the medium of heat transfer is steam. So universally is steam used that the industry is frequently referred to as the district steam industry. The Allegheny County Steam Heating Co. which operates the district heating system in downtown Pittsburgh is a subsidiary of the Du-quesne Light Co. Although organized in 1912 primarily as a means of securing the electric load of downtown buildings, the service has now become so valuable and so popular that it is no longer considered a necessary adjunct to the electric business but rather a separate business standing on its own feet. Fig 1 shows the layout of the plants and distribution system of downtown Pittsburgh. Two generating plants, one known as the Stanwix and the other as Twelfth Street, supply the area. Each has two boilers with capacity totaling 1,350,000 lb per hour. The Stanwix Plant is supplied coal by truck. The coal is pulverized at the plant and burned as powdered fuel. Coal is supplied to the Twelfth Street Plant also by truck but the boilers arc stoker fired. Over 1 1/2 miles of tunnel house a portion of our main lines, but it requires over twelve miles of pipeline, ranging in size from 32 down to 1 in. in diameter, to supply all our customers. The distribution system consists of two systems in a sense, one high and one low pressure with certain interconnections between the two. Our high pressure system supplies steam up to 125 Ib to some but not all customers, while the low pressure system operates in the range of 10 to 20 psi. Note that the two plants are tied together through large steam mains and that the system to some extent is a loop system, making it possible to have a portion of the line shut, down without interrupting service to any customer. Fig 2 conveys a picture of the extent to which steam service is used in the downtown triangle. The black area indicates the buildings which now use district steam. The dotted area indi-

Jan 1, 1950

By S. S. Arentz

PLANNED health and safety programs have become an essential part of American industry because such programs lead to increased operating efficiency, improved labor relations, better public relations, and to substantial savings in compensation insurance. Those of you who have had the unpleasant duty of informing the wife or widow of one of your men of his serious injury or death while on the job, know that all the benefits of a successful safety program do not show on the balance S. S. ARENTZ, Member AIME, is General Superintendent, Nevada Operations, Combined Metals Reduction Co., Pioche, Nevada. AIME San Francisco Meeting, February 1949. TP 2741 A. Discussion of this paper (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Jan. 6, 1949. sheet. These programs are of particular importance to the mining ,industry because mining&apos;s reputation as an unusually hazardous industry and the commonly isolated location of mining operations tend to focus attention on these problems. Description of Operations: Before proceeding with a discussion of our health and safety programs at Pioche, it may be proper to give a brief description of Pioche and of our operations there. Pioche is one of the early Nevada mining camps. It was founded shortly after the discovery of high grade silver ore in 1863 and mining has continued with more or less regularity to the present day. In an era of lawlessness, Pioche was notorious. The story persists that 75 men died with their boots on before one died a natural death, and old payroll records show that nearly as many gunmen were employed to stand off claim jumpers as there were miners working the mine. That was probably as close to a safety program as the times permitted. Pioche is situated in southeastern Nevada on the main highway between Ely and Las Vegas. The camp is on the flank of "Treasure Hill," near the original silver discovery, at an elevation of about 6000 ft. The present day population of about 2000 is primarily dependent upon the mines of the area, although Pioche also serves as the county seat of Lincoln Couqty and as the center of the surrounding livestock industry. The camp is served by a branch of the Union Pacific Railroad and receives power from the generators at Hoover Dam. The Pioche operations of the Combined Metals Reduction Co. were started in 1923 when the first complex lead-zinc ore was shipped to the company&apos;s mill at Bauer, Utah. The modern mill at Pioche was completed in 1941. The operations are medium sized in the nonferrous field, employing an average of 350 men in the mine, mill, and related works. The complex lead-zinc ore is mined from replacement deposits in a comparatively flat, extensively faulted, limestone horizon. Mining methods vary from stull-supported open stopes to filled square-set stopes. The thin bedded limestone and shale overlying the ore is allowed to cave as areas are mined out and caving frequently follows closely upon ore extraction. The relatively heavy ground and the numerous faults add to the problems of safe mining. The mine is well mechanized and the mill and surface plant are modern and well equipped. Labor is organized in a C.I.O. union and labor-management relations have been unusually harmonious. During most of the period since 1923 a competent supervisory staff worked to reduce safety hazards but the primary responsibility for safety rested on the individual workman. Accidents happened and all too frequently they were regarded by all concerned as unavoidable. In October 1939, the late Robert L. Dean became superintendent at Pioche. Most of his previous experience had been in the fields of iron and coal mining and from that experience he brought the concept that no accident is unavoidable. Many of the features of our present health and safety programs were initiated by Mr. Dean during his term as superintendent. Health Program: Our health program centers in Dr. Q. E. Fortier and his new, well-equipped, and well-staffed, modern hospital in Pioche. The program starts with a thorough pre-employment physical examination and is followed by yearly re-examinations at the expense of the company. The Pioche Mutual Benefit Association, to which all Pioche mine operators and employees belong, pays benefits covering hospitalization and surgery expense incurred by employee members and their families. The Association is governed by a board of directors elected by its members. The mine operators of the district donated the original capital and pay the monthly dues of the employee members. The employees pay the dues covering members of their families. Though not strictly a part of the

Jan 1, 1951

By Y. C. Liu, G. A. Alers

measurements of the anisotropy in Young&apos;s modulus produced in copper by rolling 95 pct reduction in thickness below room temperature have been carried out in order to study the dependence of the texture on rolling temperature. The results clearly show the transition from a copper-type texture to a brass-type texture as the temperature of rolling is lowered. The intermediate textures observed can be described very well as a simple mixture of the two terminal textures. These results cormbined with other texture measurements make possible afresh review of the experimental facts velating to rolling textures in fee metals and, as a consequence, a critical examination of the current theories is presented. PREVIOUS experiments have shown that the transition from the copper- to the brass-type rolling texture is clearly displayed and can be quantitatively analyzed by measurements of the anisotropy of Young&apos;s modulus.&apos; Application of this method to the Cu-Zn alloy system showed that the description of the texture transition as a gradual rotation of the grains from the orientation characteristic of the copper texture to the {110}(112) texture of brass2 was inconsistent with the data. Instead, the data suggested that the texture within the transition region could be described as a simple mixture of the two terminal textures.5 Unfortunately, it was difficult to establish this point conclusively because of the inadequacy of corrections for the composition dependence of the single-crystal elastic constants. Since a rigorous establishment of the nature of this texture transition is essential to our understanding of the formation of rolling textures in fee metals, it is clearly important to undertake an investigation in which the composition dependence of the elastic constants would not enter. A suitable composition-independent texture transition is provided by the well-established variation in the rolling texture of copper with rolling temperature. This temperature-dependent texture transformation has been studied by smallman&apos; in several fee alloys and by Müller5 and others"&apos; in copper. They observed that the texture characteristic of copper rolled at room temperature changed to a brass-type texture when the rolling temperature was lowered to 77°K. Although it is not possible to decide unequivocally from the published pole figures whether or not the 77°K rolling texture of copper is entirely of the brass type,&apos; this complication does not affect the main purpose of the present investigation. In addition to establishing the nature of the texture within the transition region, the modulus data should also provide a determination of the temperature at which the transition occurs as well as the temperature range over which the transition extends. This information when combined with the modulus data on Cu-Zn alloys would then provide a considerable body of new information on textures in fee metals. Since these modulus results and the data obtained from pole-figure studies must be internally consistent, it is appropriate to compile a brief summary of the experimental observations based on all available methods rather than on the pole-figure data alone as has been done in the past. The primary purpose of such a summary would be to yield a more precise definition of the experimental facts on the rolling textures of fee metals, and thus greatly facilitate our evaluation of various proposed theories in this field. The final section of this paper is devoted to this compilation of consistent, experimental facts and their application to the various theories. EXPERIMENTAL PROCEDURE Two 18-lb ingots of cathode copper of 99.99 pct purity were induction-melted under a nitrogen atmosphere in a graphite crucible and chill-cast into a steel mold. The ingots were repeatedly cold-rolled and annealed (I hr at 500°C) into slabs about 1 1/8 in. thick. Blocks 3 1/4 in. wide, 2 1/4 in. long, and 1.000 in. thick were machined from each slab. The rolling schedule used was the same as in the previous investigation1 and the final thickness of the sheet was 0.050 in. with a rolling reduction of thickness of 95 pct instead of 97.5 pct as in the previous work.&apos; The compositions and temperatures of the cold baths used for the low-temperature rolling were as shown in Table I. After each pass the rolled strip was immediately immersed in the cold bath for about 1 min or until the bubbling of the bath had subsided. The modulus data were taken within 2 hr after the rolled strip was warmed to room temperature for the first time, so that effects due to recrystallization were minimized. The modulus specimens were in the shape of flat bars, 3 in. long, 4 in. wide, and 0.050 in. thick, cut with their long dimensions oriented at 15-deg intervals between the rolling direction and the transverse direction. The values of Young&apos;s modulus were deduced from measurements of the frequency at which these long narrow bars were set into longitudinal, resonant vibration as previously described.9 To excite the mechanical vibrations in the specimen, an electromagnetic drive similar to that employed by Thompson and lass" was used. The maximum in the amplitude of

Jan 1, 1968

By L. R. Shoenberger

Boron has been used to produce nonaging low-carbon sheet steel. Retention of the necessary minimum amount of about 0.006 pet partially killed the steel. Amounts exceeding about 0.012 pet increased the degree of deoxidotion, piping tendencies, and possibility of hot tearing in primary rolling. Semikilled practice resulted in good ingot yields and satisfactory surface quality. Aluminum added with the boron provided a protective de-oxidizer. Good drawobility was indicated by performances of the steel in a limited number of deep-drawing trials. Some problems with hot-tearing and boron-analysis procedures were overcome. Metal lographically, the boron semikilled steels revealed some structures not usually found in plain low-carbon steels. IN 1943 Low and Gensamer1 reported that strain aging, which hardens and embrittles ordinary low-carbon rimmed steel, was due to nitrogen and carbon, and that oxygen played a relatively unimportant role. Since then, many investigators have substantiated their findings and indicated that nitrogen is particularly potent. Commercially, today&apos;s most widely produced non-aging sheet steels for deep drawing are either aluminum killed or vanadium rimmed types. The difference in deoxidation practice, alone, is evidence that oxygen is apparently not an important consideration in control of strain aging. The fact that nitrogen is important is apparent in the consideration that has been given, knowingly or unknowingly, to the amount combined with aluminum and vanadium. Patents were granted to Hayes and Griffis2 for the processing of aluminum-killed steel, and to Epstein" for the manufacture of vanadium rimmed material. Certain prescribed steps in producing these steels can be correlated with the formation of the respective nitrides within certain temperature ranges below the usual hot-finishing temperatures. The potential nonaging properties of either type can be reduced or suppressed by cooling too rapidly to permit the aluminum or vanadium to combine with nitrogen. Subsequent suberitical annealing of the cold-rolled strip, however, normally forms the nitrides and produces the resistance to strain aging. Titanium-killed nonaging steel, described by Comstock,1 forms a nitride in the molten state and is essentially nonaging throughout its processing. Zirconium-killed steel, which was investigated briefly by the author,* appeared to have similar nitride- forming characteristics. It is known" that chromium can produce nonaging rimmed steel, but relatively little is known of the potentialities of some of the other nitride-forming elements such as boron, silicon, columbium, and cerium. In attempting to develop a new nonaging cold-rolled sheet steel with good drawability, the following factors were considered pertinent. Such a steel would necessarily have a low carbon content and therefore have a relatively high degree of oxidation when made in a basic open-hearth furnace. If the denitriding element were also a deoxidizer, a part of the addition would be lost as oxide. The degree of deoxidation would determine whether the steel is rimmed, semikilled or killed, and also could be expected to have an important bearing on ingot yields and ultimate surface quality. Assuming that the pattern for the production of cold-rolled sheets would not be changed to any great extent, the nitride must form in the molten steel, in hot rolling, in subsequent cooling, or in annealing. The nitride, once formed, should resist dissociation and be stable in the final product. Usually an excess of the nitride-forming element is required to combine with sufficient nitrogen. If the element used is a strong ferrite strengthener, a small excess may markedly decrease drawability. With aluminum and vanadium, about 0.03 to 0.05 pct in the steel is preferred. Epstein has said" that about 0.30 pct chromium is required. Titanium nonaging steels are hard unless a sufficient amount (about 0.30 pct) is added also to combine with the carbon. The cost of the necessary amounts of these latter two elements discourages commercial acceptance. Silicon was considered as a possible nitride former, but since amounts up to 0.10 pct in rimmed and semikilled steels do not induce marked resistance to strain aging, larger amounts are apparently required, which would tend to harden and strengthen the ferrite. Of the other elements mentioned, all but boron are expensive heavy-metal elements. Stoichi-ometrically, almost an equal weight of boron would be required to combine with the nitrogen—-ordinarily about 0.003 to 0.006 pct in scrap-practice open-hearth steels. Boron is a slightly stronger deoxidizer than carbon but is less powerful than zirconium, aluminum, or titanium. Thus a rimmed-steel practice might be possible. There is much in the technical literature concerning the hardenability effects of minute amounts of boron in killed steels but very little about its behavior in low-carbon material—particularly as a ferrite strengthener. The available data indicated a need for better information concerning the effects of boron in low-carbon strip steels. Experimental Work Development of a Boron-Treated Nonaging Strip Steel—Initial attempts to produce a boron-rimmed strip steel employed 3-ton basic open-hearth heats which could be teemed into molds large enough to sustain a normal rimming action. Boron as ferro-boron was added to the ladle in small amounts because of the reported hot-short character of aluminum-killed heat-treating grades containing more than about 0.005 pct boron. Actually, the amounts used, i.e., 1/8 and 1/4 lb per ton, would be large for

Jan 1, 1959

By J. E. Dutrizac, R. J. C. MacDonald, T. R. lngraham

When sintered disks of synthetic chalcopyrite (CuFeS2) were leached in acidified aqueous solutions of ferric sulfate, the following reaction stoichiometry was obtained: CuFeS2 + 2Fe2(SO4)3 = CuSO4 + 5FeSO4 + 2S Over the temperature range from 50º to 94ºC, the reaction displayed parabolic kinetics. The parabolic rate constant for the dissolution of copper is given by the equation: log.k(mg2/cm4-hr)= 11.850 - 3780/T The activation energy for the dissolution process is 17 ± 3 kcal per mole. The parabolic kinetics have been attributed to the progressive thickening of a sulfur film on the surface of the chalcopyrite. When the leaching solutions contain less than 0.01 molar Fe+3 , the Fe concentration influences the rate of leaching, probably through a mechanism involving the diffusion of ferric sulfate through the sulfur layer. At higher Fe+3 concentrations, the rate control in the leaching. reaction has been attributed to the diffusion of ferrous sulfate through the sulfur. The rate of reaction is insensitive to changes in acid concentration and in disk rotation speed. ThE reaction of acidic ferric sulfate solutions with various sulfide minerals is of practical interest for both bacterial and heap leaching. This leaching medium is generally used with low-grade ores that cannot be treated profitably by conventional means. In both bacterial leaching1-3 and heap leaching, the active agent for sulfide dissolution is ferric sulfate. Although the reactions of ferric sulfate with chalcocite, covellite, and bornite have been investigated,4*7 the kinetics of leaching chalcopyrite with ferric sulfate have not been thoroughly studied. This paper reports a study of that reaction. EXPERIMENTAL Reagent-grade sulfur was purified by the method of Bacon and FanelliB and then it was vacuum-distilled to remove any soluble magnesium salts that had been introduced during the purification procedure.9 From stoichiometric quantities of the purified sulfur and hydrogen-reduced electrolytic copper sheet (99.90 pct Cu), CuS was synthesized at 450°C in a vacuum-sealed, pyrex vessel. About 24 hr was required for the completion of the reaction. A similar procedure involving hydrogen-reduced iron wire (99.90 pct Fe) was used to synthesize FeS1.002. A 2-furnace arrangement was required. The iron was heated to 800°C while the sulfur was maintained at about 400°C. Although the reaction to consume the sulfur was rapid, the material required additional heating (1 week) in a sealed silica ampoule at 800°C before it was homogenized. X-ray powder diffraction analysis confirmed that the copper sulfide was covellite and that the iron sulfide was troilite. The composition of the iron mineral was confirmed by wet chemical analysis. The two sulfides were ground to minus 100 mesh, weighed in equimolar amounts, mixed thoroughly, and pressed into pellets at 80,000 psi. The pellets were vacuum-sealed in pyrex ampoules and then sintered for 3 days at 550°C after an initial heating at 450°C for a few hours. The pellets were then cooled, polished with 3/0 emery paper, rinsed in acetone, and stored. The material had the characteristic brassy color of chalcopyrite and was shown by X-ray diffraction to be CuFeS2. Microscopic examination of the polished surfaces revealed small inclusions of pyrite (approximately 0.5 vol pct) as the only impurity. The presence of small amounts of a second iron compound will not alter the amount of dissolved copper but might increase the amount of ferrous ion slightly. It was calculated that dissolution of all of the pyrite and 100 mg of Cu (a typical value) would change the expected ferrous concentration by only 4 pct. Microscopic examination of a pellet after leaching revealed that the pyrite was not preferentially solubilized; only those pyrite grains at the surface were attacked. Hence, the pyrite is unlikely to alter the rate of copper dissolution. The chalcopyrite disks were about 1.7 mm thick and 27 mm in diam. They were about 80 pct of theoretical density, and for this reason their true reaction area was somewhat larger than the 5.8 sq cm area presented by the polished face. The disks were cemented to lucite cylinders in such a way that only the polished face was exposed. The disks were then leached by methods previously described.6,7 RESULTS AND DISCUSSION Stoichiometry and Kinetics. The initial experiments were directed to the problem of resolving the stoichiometry of the leaching reaction. Disks of CuFeS2 were leached at 80°C for various periods of time in acidified ferric sulfate solutions that were protected from oxidation by a cover of flowing nitrogen. When the disks had been partly leached, they were removed, their soluble salts were washed out, and then they were treated with CS2 in a Soxhlet extraction apparatus. The ratio of elemental sulfur to dissolved copper thus obtained was approximately 2 to 1. After the extraction of elemental sulfur from the pellet, the residue consisted of unreacted chalcopyrite only. For runs in which an appreciable amount of copper was dissolved, the ratio of ferrous ion to cupric ion in the solution was

Jan 1, 1970

By D. S. Flett, D. W. West

The solvent extraction of chromium 111 has been studied for the system Cr 111, H,SO., H,O/RNH/RNH., xylene, where the primary amine used was Primene JMT. Rate studies have shown that extremely long equilibrium times are required, ranging from 1 hr at 80°C to 20 days at room temperature. Heating the solution prior to extraction increases the rate of extraction. The variation in the amount of Cr 111 extracted is an inverse function of the acidity of the aqueous phase. Thus, the slow rates of extraction appear to be connected with the hydrolysis of the Cr I11 species. Extraction isotherms for the extraction of Cr 111 have been obtained for two sets of experimental conditions, namely at 60°C and for a heat-treated solution cooled to room temperature. The separation of Fe 111 from Cr 111 and Cr 111 from Cu 11 in sulfate solution by extraction with Primene JMT has been studied and shown to be feasible. A survey of the literature relating to the solvent extraction of chromium showed that, although many systems exist for extraction of Cr VI, only a very few reagents have been found to extract Cr 111. The extraction of Cr III by di-(2-ethyl hexyl) phosphoric acid has been reported by Kimura.&apos; A straight-line dependence of slope —2 was observed between log D,, and the log mineral acid concentration at constant extractant concentration. Since the slope of this plot reflects the charge on the ion extracted, it must be concluded that a hydrolyzed species of Cr III is being extracted. Carboxylic acids generally do not form extractable complexes with Cr III but di-isopropyl salicylic acie does extract Cr 111. Simple acid backwashing of the organic phase, however, failed to remove the chromium. Similar difficulty in backwashing was found by Hellwege and Schweitzer8 in the extraction of Cr I11 with acetyl-acetone in chloroform. The extraction of Cr 111 from chloride solutions by alkyl amines has been reported4-&apos; but the maximum amount of extraction achieved in these studies did not exceed 10%: From sulfate solutions, however, Ishimori" has shown that appreciable amounts of Cr I11 were extracted by amines. The amines used were tri-iso-octyl amine, Amberlite LA-1 (a secondary amine, Rohm & Haas) and Primene JMT (primary amine, Rohm & Haas). The efficiency of extraction with regard to amine type was primary>secondary> tertiary. Appreciable extraction of Cr I11 was recorded for Primene JMT as the aqueous phase acidity tended to zero. The major difficulty with Cr I11 in solvent extraction systems stems from the nonlabile nature of the ion in complex formation. This accounts for the slow rate of extraction generally experienced and the difficulty encountered in backwashing the Cr I11 from the organic phase in the case of liquid cation exchangers. Consequently, the possibility of extraction of Cr I11 as a complex anion is attractive since the backwashing problems should be minimized in this way. From published data, it appeared that the extraction of chromium from sulfate solutions of low acidity by primary amines afforded the best chance of success for a useful solvent extraction system for Cr iii This paper presents the results of a study of the extraction of Cr I11 from sulfate solution by Primene JMT and examines the application of such an extraction procedure for the recovery of chromium from liquors containing iron and copper. Experimental Chromium solutions were prepared from chrome alum in sulfuric acid and sodium sulfate so as to maintain a constant concentration of sulfate ion of 1.5 molar. Solutions of Primene JMT were prepared in xylene and the amine equilibrated with sulfuric acid/sodium sul-fate solutions, of the same acidity as the chromium solution, until there was no change in acidity between the initial and final aqueous phases. The solutions of Primene JMT conditioned in this way were then used for the equilibration experiments. Equilibrations at 25°C were carried out in stoppered conical flasks shaken in a thermostat; equilibrations at all other temperatures were carried out in stirred flasks in a thermostat. After equilibration, the phases were separated and analyzed for chromium. In the tests on the rate of extraction, small samples of equal volume of both phases were withdrawn from time to time and the chromium distribution determined. The chromium analyses were carried out either coloi-imetrically using diphenyl carbazide, or volu-metrically using addition of excess standard ferrous ammonium sulfate and back titration of the excess iron with potassium dichromate. The oxidation of Cr 111 to Cr VI in the case of the raffinate solution was effected by boiling with potassium persulfate in the presence of silver nitrate and, for the backwash solution, by boiling with sodium hydroxide and hydrogen peroxide. Results Preliminary experiments indicated that extraction results were effected by the age of the chromium solution, higher distribution coefficients being obtained with solutions which had been allowed to stand for some time. Consequently a stock solution of chrome alum, 10 m moles per 1 Cr I11 in 1.4 M Na,SO,/O.l M &SO,,

Jan 1, 1971

By C. W. Binckley, F. R. Burgess, E. R. Haymaker

A method of establishing stabilized back-pressure curves for gas wells producing from formations of extremely low permeability is presented. Actual well performance under many different operating conditions is shown by the stabilized back-pressure curve. By use of the method. it is possible to conduct back-pressure tests with a critical-flow prover on wells that stabilize slowly, and save approximately 88% of the gas ordinarily vented to obtain satisfactory test data, with a great reduction in time required for testing. INTRODUCTION The reasons for establishing dependable back-pressure curves on gas wells have been pointed out by previous publications. The publication most referred to. of course, is the United States Bureau of Mines Monograph 7, titled "Back-Pressure Data on Natural Gas Wells and Their Application to Production Practices". The technique generally established therein has been accepted and used by many engineers; and, when proper tests are conducted, the results can be used for the analysis and solution of several practical problems concerning field operation and development. Even where formations of low specific permeability are encountered, the determination of a well&apos;s actual performance by the back-pressure test method permits the engineer to analyze many problems in individual well operation and also to predict necessary future field development. Such problems as the determination of the ability of a well to produce into a pipe line at a predetermined line pressure, the design of gas gathering systems and meter settings, and the determination of the time and the number of wells required to be drilled to meet future market obligations, can be solved, in part., by the use of a reliable back-~ressure curve. In addition, the computed well delivery rates determined by data from backpressure tests ordered by state regtilatory bodies, when compared with the true back-Pressure curve, permit the operator to ascertain whether such data represent unstable or relatively stabilized delivery rates for given pressure conditions of the well. The technique of back-pressure testing, as described in this report, was developed by Phillips Petroleum Company engineers from data obtained during a testing program that started in 1944 and has been continued to date. Three hundred and eleven back-pressure tests were conducted on 299 wells located in the southern part of the Hugoton Field. The gas-bearing zone is composed of several dolomitic formations of the Permian Age; the important ones are the Herington, Upper Krider, Lower Krider, and Winfield. The average bottom-hole temperature is approximately 91 °F.. and the initial wellhead shut-in pressures range from 400 to 440 psig. The spacing pattern is 640 acres per well with each well located near the center of the section. The range of back-pressure potentials on wells tested was from 500 to 23,000 Mcfd. All gas wells were acidized, and the quantity of acid used, expressed in 1574 hydrocloric acid, varied from 12,000 to 22,000 gallons per well. The quantity and concentration of each treatment depended on the stage, the formation being treated, and experience gained from previously completed wells. The gas in the Hugoton Feld is a "dry" gas. It has a gasoline content of approximately 0.25 gallons per thousand cubic feet, as determined by charcoal test, and its specific gravity averages about 0.71 as compared to air (air = 1.00 at 60°F.). Of the wells tested, 71 were completed with 7" casing, 3 with 9 5/8" casing, and 1 with 6%" casing set on top of the upper producing formation with the well bore through the gas bearing formations being open hole. Two hundred and twenty-four were completed with 5 1/2&apos;&apos; O.D. casing set through the gas bearing formations and perforated. For the purpose of establishing reliable back-pressure curves in the area, Phillips Petroleum Company personnel has computed data on the basis of 24-hour flows per point. Early in the program, many tests were actually permitted to flow 24 hours to obtain data for each plotting point, at great expense in man power and time. Presently, however, such tests have been replaced by tests of short duration flows which can be made to effect results that correspond to the tests obtained by flows of much longer duration. METHOD When a gas well producing from a reservoir of low permeability is opened for production through a constant size orifice, both the rate of flow and working pressure decline. first at a high rate and later at a lower rate until after several hours the decline becomes difficult to ascertain. In this paper the rae of flow and working pressure are considered to be stabilized when it becomes difficult to observe changes in working pressure during a period of three hours by the use of a deadweight pressure gage. Stalibization of pressure in the literal sense is never obtained in a producing gas well. In formations of low permeability. such as those in the Hugo-ton Field, most wellhead working pressures approach stabilization closely enough to be used satisfactorily in the determination of a back-Pressure potential curve after flow periods of 24 hours. We shall therefore describe the backpressure curve calculated from ohserved rates of flow and working pressure at the end of 24-hour flow periods.

Jan 1, 1949

By E. R. Haymaker, C. W. Binckley, F. R. Burgess

A method of establishing stabilized back-pressure curves for gas wells producing from formations of extremely low permeability is presented. Actual well performance under many different operating conditions is shown by the stabilized back-pressure curve. By use of the method. it is possible to conduct back-pressure tests with a critical-flow prover on wells that stabilize slowly, and save approximately 88% of the gas ordinarily vented to obtain satisfactory test data, with a great reduction in time required for testing. INTRODUCTION The reasons for establishing dependable back-pressure curves on gas wells have been pointed out by previous publications. The publication most referred to. of course, is the United States Bureau of Mines Monograph 7, titled "Back-Pressure Data on Natural Gas Wells and Their Application to Production Practices". The technique generally established therein has been accepted and used by many engineers; and, when proper tests are conducted, the results can be used for the analysis and solution of several practical problems concerning field operation and development. Even where formations of low specific permeability are encountered, the determination of a well&apos;s actual performance by the back-pressure test method permits the engineer to analyze many problems in individual well operation and also to predict necessary future field development. Such problems as the determination of the ability of a well to produce into a pipe line at a predetermined line pressure, the design of gas gathering systems and meter settings, and the determination of the time and the number of wells required to be drilled to meet future market obligations, can be solved, in part., by the use of a reliable back-~ressure curve. In addition, the computed well delivery rates determined by data from backpressure tests ordered by state regtilatory bodies, when compared with the true back-Pressure curve, permit the operator to ascertain whether such data represent unstable or relatively stabilized delivery rates for given pressure conditions of the well. The technique of back-pressure testing, as described in this report, was developed by Phillips Petroleum Company engineers from data obtained during a testing program that started in 1944 and has been continued to date. Three hundred and eleven back-pressure tests were conducted on 299 wells located in the southern part of the Hugoton Field. The gas-bearing zone is composed of several dolomitic formations of the Permian Age; the important ones are the Herington, Upper Krider, Lower Krider, and Winfield. The average bottom-hole temperature is approximately 91 °F.. and the initial wellhead shut-in pressures range from 400 to 440 psig. The spacing pattern is 640 acres per well with each well located near the center of the section. The range of back-pressure potentials on wells tested was from 500 to 23,000 Mcfd. All gas wells were acidized, and the quantity of acid used, expressed in 1574 hydrocloric acid, varied from 12,000 to 22,000 gallons per well. The quantity and concentration of each treatment depended on the stage, the formation being treated, and experience gained from previously completed wells. The gas in the Hugoton Feld is a "dry" gas. It has a gasoline content of approximately 0.25 gallons per thousand cubic feet, as determined by charcoal test, and its specific gravity averages about 0.71 as compared to air (air = 1.00 at 60°F.). Of the wells tested, 71 were completed with 7" casing, 3 with 9 5/8" casing, and 1 with 6%" casing set on top of the upper producing formation with the well bore through the gas bearing formations being open hole. Two hundred and twenty-four were completed with 5 1/2&apos;&apos; O.D. casing set through the gas bearing formations and perforated. For the purpose of establishing reliable back-pressure curves in the area, Phillips Petroleum Company personnel has computed data on the basis of 24-hour flows per point. Early in the program, many tests were actually permitted to flow 24 hours to obtain data for each plotting point, at great expense in man power and time. Presently, however, such tests have been replaced by tests of short duration flows which can be made to effect results that correspond to the tests obtained by flows of much longer duration. METHOD When a gas well producing from a reservoir of low permeability is opened for production through a constant size orifice, both the rate of flow and working pressure decline. first at a high rate and later at a lower rate until after several hours the decline becomes difficult to ascertain. In this paper the rae of flow and working pressure are considered to be stabilized when it becomes difficult to observe changes in working pressure during a period of three hours by the use of a deadweight pressure gage. Stalibization of pressure in the literal sense is never obtained in a producing gas well. In formations of low permeability. such as those in the Hugo-ton Field, most wellhead working pressures approach stabilization closely enough to be used satisfactorily in the determination of a back-Pressure potential curve after flow periods of 24 hours. We shall therefore describe the backpressure curve calculated from ohserved rates of flow and working pressure at the end of 24-hour flow periods.

Jan 1, 1949