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By George Gauci

INTRODUCTION The Broken Hill orebody was discovered in 1883. The richness of the deposit encouraged rapid development of the field and within fifteen years ten mining companies were operating. By 1940, several companies located in the centre of the field with limited reserves, had ceased operation. These leases have been acquired by Broken Hill South Limited and North Broken Hill Limited. The four companies currently operating in the field are, in order of increasing production rate:¬- Broken Hill South Limited (BH South) North Broken Hill Limited (North BH) The Zinc Corporation, Limited (ZC) and New Broken Hill Consolidated Limited (NBHC) The tonnages treated by each company since the present plants have been in operation are shown in Figure 1. The leases are located as shown in Figure 2, and an aerial view of Broken Hill showing the spread of the City on each side of the line of lode is shown in Figure 3. The present treatment plants date back to the early 1930's when the BH South plant was built. The North BH and ZC plants were built in 1939 and NBHC's in 1952. The three plants built before 1940 have similar crushing and grinding flowsheets. NBHC differs in that it includes rod mills with consequent differences in fine crushing equipment.

Jan 1, 1970

By E. Baker, David Donoghue

Legal and legislative matters constituted the outstanding features of proration in Texas in 1932. From East Texas emanated most of the political, legal, technical and industrial activity. Conroe and Thompson developed into fields of major importance. Proration orders were issued by the Railroad Commission on many of the producing fields of the Gulf Coast and West Texas not covered in previous years. In Yates, Penn Pool, Winkler, Van, the Panhandle, North Texas and West Central Texas there were 110 changes of importance, except in allowables. New proration schemes were introduced in East Texas, Conroe, Thompson, Saranosa, Government Wells, Tuleta and Howard-Glasscock. Little progress was made in administration or technical development. Legal and Legislative Matters Proration first began in Texas in 1927 as a voluntary attempt to divide the market outlet of a field on an equitable basis. The statutes then in existence were considered somewhat archaic and the Railroad Commission's authority was limited. Subsequent efforts to strengthen the laws were not wholly successful. The 1929 Conservation Act made no mention of market demand but declared that the term "waste" did not mean " economic waste." With the passage of the Pipc Line Act of 1930, providing for ratable purchasing, it was the opinion of many lawyere that a legal means of proration had been found. The 1931 law had ths same provision as that of 1929 with respect to economic waste but specifically prohibited limiting of production to market demand. The law passed Nov. 12, 1932, omitted reference to economic waste and specifically provided for limitation of production to reasonable market demand. Vigorous attacks were being made in State and Federal Courts on the constitutionality of the laws and the validity of the Commission's orders. In Peoples Petroleum Producers, Inc. et al. vs. Lon A. Smith et al., which had been heard before a three-judge U. S. District Court in Houston on May 28, 1932 and again on Sept. 19, the Court's decision for plaintiffs, released Oct. 2, influenced in a large measure the calling of the Legislature and the passage of the Market Demand Law on Nov. 12.

Jan 1, 1933

By M. Herman, G. J. London

A series of dilute Fe-Co alloy specimens were prepared from zone-melted iron. The iron used was given ten floating-zone passes in purified hydrogen. Alloying was accomplished by plating a gradient of metallic cobalt onto a 1/4-in.-diam bar of material from a pure plating bath. The deposit was radioac-tively tagged by a small addition of co80 to the plating bath. Alloy homogenization was accomplished by passing an additional floating-zone pass through the plated section of the bar. The final concentration gradient achieved was from residual to about 1000 ppm (0.1 pct) added Co. After homogenization, the bar was swaged to 0.057 in. wire and cut to tensile specimen blanks 1-1/16 in. long. Each specimen was counted in a well-type scintillation counter. The concentration of cobalt was computed by combining the normalized specimen counting rate with the known weight (measured to the nearest 0.01 mg) of cobalt added during plating. Fig. 1 shows the cobalt gradient obtained, exclusive of residual cobalt which was estimated by neutron-activation analysis to be approximately 50 ppm. Results of recrystallization for 1 hr at 750°, 700°, 650°, and 600°C with specimens containing 40, 170, 470, and 870 ppm added Co are shown in Figs. 2, 3, 4, and 5. Recrystallization was accomplished in a dynamic vacuum of less than 1 x 10 torr. The specimens were mounted and polished parallel to the swaging direction. The recrystallization re- sults show a radical coarsening of structure with increasing cobalt concentration. The coarsest structure obtained was at the 470-ppm level (at all recrystallization temperatures) with a slight grain refinement at the 870-ppm level shown. A more normal solid-solution effect is seen in Fig. 5 (60OoC, 1 hr) where the only specimen completely recrystallized is the one containing 47 ppm Co. Since the possibility existed that some atmosphere-contamination phenomenon might be responsible for the observed results the recrystallization series was repeated using sealed quartz capsules. These were filled with purified argon which was gettered during heat treatment on metallic titanium included in the capsules. The results obtained were essentially the same as shown. Another identical alloy was made using a 5-mm-diam bar of Westinghouse Puron. Specimen preparation and recrystallization treatment were also as described. The results obtained (see Table I) were somewhat erratic. Some coarsening in structure does appear at the highest cobalt concentrations. There is no apparent relationship between the coarse, columnar, directionally solidified structure of the as-melted bars and any of the recrystallized grain structures observed, all of which are much finer than the former structure. A recrystallization process can be most simply described as one of homogeneous nucleation of recrystallized grains in a cold-worked matrix followed by more or less uniform growth of the strain free grain into the cold-worked material.' An impurity element may influence one or both of these processes. Aust and utter' have shown that impurities strongly influence grain boundary mobility in lead. Moreover, definite recrystallization textures are produced by small concentrations of tin,3 while additions of silver or gold4 produce large boundary in-

Jan 1, 1964

By E. M. Elkin, J. H. Schloen

All known methods of treating and recovering the various components of copper refinery slimes are discussed. The slimes treatment processes presently used by five copper refineries are described and flowsheets are given. A bibliography is appended. THE recent increase in anode copper production at the Noranda smelter placed an additional load on the Montreal East plant of Canadian Copper Refiners Limited. The consequent increase in the amount of anode slimes led to a careful consideration of the various methods of slimes treatment. A critical review of these methods is presented here in the belief that it would be of interest to copper refiners. No such review has yet been published, although a number of individual flowsheets have been described. To make the information of greater value, a questionnaire was sent to all copper refineries. While the overall response to the questionnaire was not entirely satisfactory, the foreign refiners gave much detail in their answers and expressed willingness to cooperate further if needed. Although the data below do not cover all refineries, it is thought that examples of all flowsheets currently in use are included. A comparison of these flowsheets should prove of interest. The paper is divided into two parts. One part deals with a discussion of all known methods of treating and recovering the various components of the slimes. The second describes the processes now in use at various copper refineries for the treatment of raw slimes up to the production of Doré bullion. A brief description of the two main electrolytic methods of parting Doré bullion is appended. Since the first commercial application of electrolytic refining of copper by J. B. Elkington in 1865, the treatment of anode mud or slimes has undergone many changes. The object of treating slimes has always been the recovery and separation of precious metals. With the passage of time, increasing attention has been paid to improvement in recovery and quality of byproducts, mainly selenium and tellurium. The original methods of treatment were crude, although relatively direct. For example," the slimes were fused on a dolomitic clay bed in a reverbera-tory furnace; the slag was removed and the resulting metal cupelled to silver and gold. In another process, the dried slimes were oxidized and scorified on the lead bath of a cupelling furnace. Later, these pyrometallurgical methods were modified by sulphuric acid leaching, followed by fusion with niter in a reverb eratory furnace. A preliminary oxidizing roast improved the leaching step. Straight hydro-metallurgy has not found practical application. No matter what method is employed, the result is Dorb metal—a silver-gold alloy, with or without the metals of the platinum group. Characteristics of the Slimes Anode slimes are made up of those components of the anodes which are not soluble in the electrolyte. They contain varying quantities of copper, silver, gold, sulphur, selenium, tellurium, lead, arsenic, antimony, nickel, iron, silica, etc. The color of raw slimes is grayish black and the particle size is —200 mesh. However, Baraboshkin and Gaev (Ref. 1, p. 37), describe light gray colored slimes from the electrolysis of secondary copper which are composed predominantly of sulphates and of basic salts. In anode furnace practice primary and secondary metals are not usually segregated and such slimes do not commonly occur. Copper in the slimes originates to a large extent in the cuprous oxide of the anodes and is therefore dependent on the oxygen content of the latter: Cu2O + H2SO4 + CuSO4 + H2O + Cu [I] Opinions have been expressed that some of the copper is formed by decomposition of cuprous to cupric sulphate Cu2SO4 ? CuSO4 + Cu PI The product of either reaction is very finely divided. Depending on the slimes composition, much of the copper is combined with sulphur, selenium, tellurium, etc. The balance of the copper is in the free metallic state.

Jan 1, 1951

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

A. U. Seybolt (General Electric Research Laboratory)—The authors should be commended for adding some important information to our knowledge of the solubility of interstitial elements in metals. It is becoming increasingly evident that the effect of even traces of such elements have very far-reaching effects upon the mechanical properties of the body centered cubic metals. Those who have worked in this area know that the accurate determination of the small solid solubility limits in systems of the type reported by the authors is a quite difficult task, and it is therefore not surprising that frequently the results of different workers are not in agreement. It is instructive, and usually helpful, to plot the solubility results on log weight or atomic percent -1/T coordinates to find out if a straight line is obtained. A straight line is expected because in systems displaying solubilities of the order of 1 to 3 at. pet or less, Henry's law is usually obeyed—or at least well enough obeyed so that the deviation from linearity is not very appreciable. If Henry's law is obeyed, one canthen use the Van't Hoff Equation in the form In N = ?H/RT + C, where N is mole fraction, at. pet, or wt pet for small values, and AH is the partial molal heat of solution of the solute. R and T have the usual significance, and C is an integration constant. If one plots the reported nitrogen solubility values as indicated above, the three points fall reasonably well on a straight line. The oxygen values for the two upper temperatures fall very closely to the nitrogen values as shown in the authors' Fig. 15. However, the value at 500°C departs widely from the straight line established by the data at 1500" and 1000°C. It is, of course, true that one cannot place too much emphasis on the significance of a line established by only three points, but in the absence of reasons for anticipating deviations, data exhibiting wide departures from linearity should at least be examined closely. Fig. 16 shows the log at. pct -1/T plots for the authors Ta-O and Ta-Ndata including a solid circle point at 500°C and 1.8 at. pet for Ta-O, which is simply extrapolated from the two higher temperature points. In addition, the data of R. P. Elliott9 for Nb-O are shown. These points were picked off his curve and are not very exact, but as can be seen they line up well on a straight line. It is interesting, and probably significant, that the slope of Elliott's results is not far from those of Vaughn, et al. This is probably to be expected because one would anticipate that the partial molal heats of solution of oxyten in these two very similar metals should be not too far apart. AH for Ta-O is about -1900 cal per mol, while for Nb-O it is near -2300 cal per mol. Hence, this lends some support to the thesis that the point at 500°C for Ta-O is much too high. The data of Gebhardt and Preisedanz10 are also plotted, and it is seen that their data while lying on a linear plot, have an appreciably steeper slope. The possible reasons for this will not be discussed here except to point out that their pressure-composition data show anomalies which suggest that they may have been dealing with a different equilibrium from that being discussed. There is another consideration which would also suggest that the solubility at 500°C is lower than shown. The solubility values were obtained by the classic method of first establishing a lattice parameter-composition curve. This the authors did, and there is probably little doubt that it is quite accurate. Such a plot is generally almost error-free because it has a self-correcting feature in that any deviation from linearity makes a data point immediately suspect, and subject to confirmation. Unfortunately, this is not true with respect to the actual solubility values. These are obtained ordinarily by taking an alloy containing more solute than is soluble at some temperature and then thermally

Jan 1, 1962

By J. Walter Snavely

PRESENT-DAY processing in many industries, calcining, sintering, briquetting, beneficiation and nodulizing, increasingly calls for the handling of large volumes of hot bulk materials. Various types of conveyors have been employed. This discussion will cover the factors governing their selection. For temperature ranges up to 400°F, or approximately 200°C, a wide range of conveyors is available. Special constructions of rubber conveyor belts. steel conveyor belts, vibrating and shaker conveyors, apron conveyors, and drag chain conveyors, all are used successfully. As temperatures go well above 400°F, however, choice of conveyors is narrowly limited. This paper will consider the problem of handling bulk materials only where the temperatures exceed 400°F.

Jan 5, 1953

In the examination of an undeveloped prospect a decision must be arrived at from an inspection of the outcrops and the exposures in a few shallow pits. Prospects that are offered for sale rarely expose any important quantity of good ore, work having usually been stopped when the immediate exploration no longer yielded favorable results. It should be borne in mind, furthermore, that a great majority of prospects have been examined many times, and if of conspicuous promise, would have been acquired-for development. In most cases the problem for the engineer, therefore, is to discover the traces of a valuable mineralization that has disappeared through solution, or the conditions that indicate the possibility, or probability, of underlying secondary enrichments. The available data being meager, every feature should be the subject of careful study-the condition of the outcrop, the structural relationships, the associations of minerals, the alterations of wall rocks, the chances for underlying enrichments, and so forth, as well as the actual assay value of the material exposed. It is frequently advisable to spend the time and money necessary to have trenches dug at various significant points along a promising outcrop; such exposures, even if the depth attained is slight, often disclose conditions that are not apparent at the actual surface, as for example, the existence of soft minerals and the distribution of the various minerals through the mass of the deposit. Trenches also permit samples to be taken from points that were not accessible during former examinations. Strong, persistent outcrops of uniform width may be taken to indicate the probable size and character of the underlying vein,

Jan 1, 1932

By H. LeChatelier, B. Bogitch

Page Introduction........................... 134 Methods of Investigation....................... 135 The Tridymite Network...................... 137 Independent Variables....................... 146 Manufacturing Operations..................... 153 Introduction Silica brick are indispensable in the manufacture of steel because they alone are able to withstand the high temperature of regenerative furnaces. All attempts to replace silica brick by other refractory materials for this purpose have failed, but the reason for this failure has remained obscure; we shall give an explanation later in this paper. Before the war, silica brick employed in France came principally from abroad, for which reason, since the beginning of hostilities, certain French steel works have been seriously handicapped. Our attention was first directed to the question by M. Bied, Engineer of the Teil Works. With him, we began certain investigations, at first using our laboratory and the furnaces of neighboring steel works. The larger part of our experiments, however, have been made in the laboratory of the Faculty of Sciences at the Sorbonne. For the heating of our samples, we are deeply obliged to MM. Charpy, Yeatmann and Guerineau. In undertaking these studies, our first aim has been to render assistance to French industry, by indicating, as precisely as possible, the necessary conditions for the manufacture of high-grade brick; but at the same time me have

Jan 1, 1919

By Louis Moyd

The Concrete Research Division, U.S. Corps of Engineers, has developed a simple procedure for determining the coefficients of linear thermal expansion of rocks by means of resistance wire (SR-4) strain gauges. Gauges are cemented to the surfaces of specimens, which are then brought alternately to temperatures of 35OF and 1350F. Results are accurate to the seventh decimal place. IN the course of investigations of the thermal properties of various rocks proposed for use as aggregates in concrete structures, a relatively rapid method of determining coefficients of linear thermal expansion was required. A method which proved to be satisfactory for this purpose was developed in the petrographic laboratory of the Concrete Research Division, U.S. Corps of Engineers, at Clinton, Miss. The method is based on the fact that strain effects in a specimen can be determined by measuring variations in the resistance of an electrical conductor firmly cemented to the surface of the specimen. Equipment for the determination of strain, electrically, has been developed by the Baldwin-South-wark Division of the Baldwin Locomotive Works in Philadelphia. This equipment includes small strain gauges made of coils of resistance wire bonded between thin sheets of paper (SR-4 gauges), and a portable "Strain Indicator" which records variations in the length of the gauges in microinches per inch. Gauges of this type are now in general use for determinations of various mechanically-induced strains, but their use for the determination of coefficients of thermal expansion appears to be a new application. The advantages of the method are that the test specimens may be relatively small and require only a minor amount of preparation, that a large number of tests can be run at the same time, and that the installation and operation of the equipment is relatively simple. The method and equipment described are now in regular use for determining the coefficients of linear thermal expansion of rock samples submitted to this laboratory. Rocks which have been tested include granites, syenites, gabbros, and other igneous rocks, limestones and dolomitic limestones, sandstones, and quartzites. Specimen Preparation: To standardize the conditions of the tests, the rock specimens are sliced by diamond saw into slabs about 11/2x11/4 in. In the case of bedded or foliated rocks, three oriented slabs are cut from the same specimen, and represent, respectively, a direction in a plane of the bedding or foliation of the rock; a direction along the bedding or foliation and at a right angle to the first; and a direction across the planes of bedding or foliation. One of the large surfaces of each slab is lapped for a few minutes with No. 100 abrasive powder to remove saw scars and irregularities. The slabs are soaked in petroleum ether and then dried in an oven to remove all traces of oil picked up in the sawing

Jan 1, 1951

By Louis Moyd

The Concrete Research Division, U.S. Corps of Engineers, has developed a simple procedure for determining the coefficients of linear thermal expansion of rocks by means of resistance wire (SR-4) strain gauges. Gauges are cemented to the surfaces of specimens, which are then brought alternately to temperatures of 35OF and 1350F. Results are accurate to the seventh decimal place. IN the course of investigations of the thermal properties of various rocks proposed for use as aggregates in concrete structures, a relatively rapid method of determining coefficients of linear thermal expansion was required. A method which proved to be satisfactory for this purpose was developed in the petrographic laboratory of the Concrete Research Division, U.S. Corps of Engineers, at Clinton, Miss. The method is based on the fact that strain effects in a specimen can be determined by measuring variations in the resistance of an electrical conductor firmly cemented to the surface of the specimen. Equipment for the determination of strain, electrically, has been developed by the Baldwin-South-wark Division of the Baldwin Locomotive Works in Philadelphia. This equipment includes small strain gauges made of coils of resistance wire bonded between thin sheets of paper (SR-4 gauges), and a portable "Strain Indicator" which records variations in the length of the gauges in microinches per inch. Gauges of this type are now in general use for determinations of various mechanically-induced strains, but their use for the determination of coefficients of thermal expansion appears to be a new application. The advantages of the method are that the test specimens may be relatively small and require only a minor amount of preparation, that a large number of tests can be run at the same time, and that the installation and operation of the equipment is relatively simple. The method and equipment described are now in regular use for determining the coefficients of linear thermal expansion of rock samples submitted to this laboratory. Rocks which have been tested include granites, syenites, gabbros, and other igneous rocks, limestones and dolomitic limestones, sandstones, and quartzites. Specimen Preparation: To standardize the conditions of the tests, the rock specimens are sliced by diamond saw into slabs about 11/2x11/4 in. In the case of bedded or foliated rocks, three oriented slabs are cut from the same specimen, and represent, respectively, a direction in a plane of the bedding or foliation of the rock; a direction along the bedding or foliation and at a right angle to the first; and a direction across the planes of bedding or foliation. One of the large surfaces of each slab is lapped for a few minutes with No. 100 abrasive powder to remove saw scars and irregularities. The slabs are soaked in petroleum ether and then dried in an oven to remove all traces of oil picked up in the sawing

Jan 1, 1951

By Tasuku Fuwa, John Chipman, David H. Kirkwood

Fe-C-Si alloys in silica crucibles were held at 1600°C in a controlled atmosphere of CO and Co2 and the approach to equilibrium was obsertsed. Results were not of sufficient precision to establish the activity and interaction coefficients. Observations 012 the equilibrium provided an average value for the standard free-energy change which differed by + 1.1 kcal from the earlier accepted value. The C-SL relation at other temperatures is calculated and shown graphically. IN the refining of steel in an acid-lined furnace, it is well known that, unlike in basic refining, a very significant amount of silicon may remain dissolved in the metal even when the carbon content approaches a final endpoint. Further, it is known that the residual silicon increases with increasing temperature. The quantitative relation between silicon and carbon can be calculated for equilibrium conditions from data already available on the Fe-C-O and the Fe-Si-O systems. Such equilibrium calculations could show us approximately the limitations within which the reaction would be expected to operate in practice. In the oxidation of a bath containing both carbon and silicon it is well known that at low temperatures silicon is preferentially oxidized first. It can be shown by calculation that at high temperatures carbon will be oxidized preferentially. It is the purpose of this paper to record direct observations on the Si-C relation by means of experiments carried out in an atmosphere of carbon monoxide for Fe-C-Si alloys contained in silica crucibles. When such a system is brought into equilibrium, at a fixed temperature, the composition of the liquid metal is governed by the following equations: Both K1 and K2 are known with a fair degree of accuracy, and may be calculated from the tabulated In general the percentage of CO2 is extremely small compared to that of CO and in the experiments to be described the partial pressure of the latter was generally only slightly below 1 atm. EXPERIMENTAL METHOD The induction furnace employed was the same as that described by Rist and chipman' and by Fuwa and chipman.2 It was modified slightly in view of the change from alumina to silica crucibles. The small silica crucible was surrounded by a thin susceptor of molybdenum sheet which in turn rested inside a zirconia crucible. Since the zirconia was subject to breakage, it was supported inside an alumina crucible. The charge consisted of 30 to 35 g of electrolytic iron along with the required amounts of refined silicon and graphite to produce a melt of required composition. Purified carbon monoxide and carbon dioxide were passed into the furnace through carefully calibrated flow meters. Two separate and independent series of experiments were carried out. In Series I (D.H.K.) the melt was held in the furnace at 1600°C for periods of time up to 6 hr. Samples were taken at intervals in silica tubes and were analyzed for carbon and silicon. The results of the last one or two samples taken from each experiment and the direction in which equilibrium appeared to be approached are shown in Table I. In Series II (T.F.) the silica crucibles were of less satisfactory strength and the melts were held at 1600° C for periods of only 2 to 4 hr. In heats number 29 to 45 inclusive, the metal was cooled in the furnace and the ingot itself served as a sample for analysis. In heat 46 and all subsequent heats, samples were withdrawn in silica tubes at the termination of the heat, and these samples were analyzed. The results of all of these experiments in which equilibrium appeared to be approached are listed in Table II.

Jan 1, 1965

By L. A. Dale, D. A. Dahlstrom

Closed-water circuits are justified today from two standpoints: economical operation and prevention of stream pollution. In today's modern preparation plant, it has been found very desirable to have the plant circulating water maintained at a relatively low solids concentration of around 3%. In so doing, bene-ficiation equipment can operate at a much higher efficiency. However, makeup water requirements would become excessive if the fines were to be removed from the preparation plant by bleeding a 3% solids concentration to a tailings pond. With the ever increasing percentage of —200 mesh coal, clay and slimes in the raw coal, coupled with the creation of these fines within the preparation plant, the need for water conservation for economy reasons becomes even more important. Because of stream pollution laws, tailings ponds have become very costly to operate and maintain, resulting in the necessity of employing an in-plant method of water recovery. Accordingly, the primary system employed in water recovery in the coal preparation plant today consists of a solids concentration device to thicken refuse solids while at the same time producing a sufficiently clarified effluent that can go back to the preparation plant for water reuse. The thickened product is then normally passed to a dewatering device that will produce a handleable solid that can be disposed of

Jan 1, 1965

By R. J. Sandrea, S. M. Farouq Ali

The results of an experimental and theoretical study of the effects of rectilinear impermeable barriers and highly permeable channels on the sweep efficiency and conductivity of a five-spot network are presented. The study was carried out using Hele-Shaw, and conductive sheet analogs for both. normal and inverted flood patterns. A functional relationship was developed which provides quantitative prediction of the above parameters; i.e., sweep efficiency and conductivity, for the nonhomogeneous system. To evaluate this, it is necessary only to measure the interference modulus of the obstacle using a simple expression. The results indicate that impermeable barriers, with an interference modulus greater than zero, always cause a decrease in the conductivity and the sweep efficiency of the pattern. On the other hand, permeability channels do not have a significant effect on these parameters, unless they are located along the streamlines. The study also discusses a method of formulating the difference equations pertaining to the two-dimensional Laplacian in a system containing rectilinear barriers. In addition, a technique is described for tracing the progress of a free surface, using marked particles, in a stream containing discontinuities SuCh as those occurring at the extremities of barriers. The above computational scheme was used in a digital computer program to simulate results of the Hele-Shaw analog. The computed values of sweep efficiency mere in good agreement with the experimental values. INTRODUCTION At the present time waterflooding remains the most widely used technique for the secondary recovery of oil. Among the numerous factors that affect the performance of a waterflood, the areal sweep efficiency constitutes one of the most critical parameters. It is a function only of the geometric distribution of the wells for a homogeneous medium and unit mobility ratio. Geological considerations, however, such as the presence of sealing faults or solution channels in the rock matrix, would generally exert an adverse effect on the areal sweep efficiency of a waterflood network. Surprisingly little information is presently available on the quantitative implications of such permeability interferences. It was the object of this investigation to consider the presence of rectilinear, impermeable and highly permeable interferences in an otherwise homogeneous five-spot pattern, and to analyze their effects on the resulting sweep efficiency and pattern conductivity. The experimental phase of the study was conducted using two different models: the Hele-Shaw flow cell and the field plotter. For experimental convenience, the geometric boundaries of the five-spot were assumed to constitute streamlines even in the case where the interference was asymmetrically placed with respect to a repeated five-spot pattern. A second object of the study was to develop a computational scheme for numerically calculating the pressure distribution in a five-spot flow pattern containing rectilinear, impermeable barriers, and to use this distribution to compute the sweep efficiency. EXPERIMENTAL PROCEDURE HELE-SHAW ANALOG The Hele-Shaw analog was used both as a visual model and for determining the sweep efficiency for systems involving impermeable barriers. The physical limitations of this model as a means of experimentally studying the motion of a fluid in porous medium have been adequately discussed elsewhere.2,7 Likewise, it can be easily verified that the analogy remains valid when a portion of the region between the plates contains an obstacle of the same thickness as the distance between the plates. The model used in this study was composed of

By Richard J. Fruehan

ThE thermodynamic activities of nickel and chromium in liquid Ni-Cr alloys have not been previously reported. There have been several investigations on the solid alloys.1-3 In the present investigation the activity of chromium in liquid Ni-Cr alloys at 1600° C was determined by the use of the following galvanic cell, The use of galvanic cells employing solid oxide electrolytes for determining the activity of metals in solid alloys was first demonstrated by Rapp and Maak4 on Cu-Ni alloys between 700° and 1000°C. Recently Schwerdtfeger5 tested the performance of the ZrO2(CaO) electrolyte at 1600°C and found it satisfactory for oxygen pressures as low as 10"12 atm. He also demonstrated the use of solid oxide electrolytes for determining the activities in liquid metal systems in measuring the activity of manganese in Fe-Mn alloys at 1500°C. Extensive investigations have been carried out in this laboratory, exploring the oxygen partial pressure lower limit at which ZrO2(CaO) electrolyte can be used satisfactorily in oxygen galvanic cells at 1600°C. In a paper to be published at a later date,9 it is demonstrated conclusively that ZrO2(CaO) exhibits insignificant electronic conductivity at oxygen pressures down to about 3 x 10"13 atm which is lower than the oxygen partial pressure in equilibrium with Cr-Cr2O3 at 1600°C. Therefore, the activity of chromium can be related to the measured reversible electromotive force of the cell in the present investigation since no electronic short circulating will occur. Fig. 1 is a schematic diagram of the cell used. The Cr-Cr2O3 electrode was made of equal weights of chromium and Cr2O3 powders which were mixed and packed into a recrystallized alumina crucible. A Pt-wire lead was embedded into the Cr-Cr2O3 compact to insure good contact. A ZrO2(CaO) crucible, supplied by the Zirconium Corp. of America, contained the Ni-Cr melt equilibrated with solid Cr2O3. The ZrO2(CaO) crucible was placed on the Cr-Cr2O3 electrode and additional Cr-Cr2O3 mixture was packed around it. Contact with the Ni-Cr alloy was made with a Cr2O3 tube, which is a weak electronic conductor. A platinum wire lead was attached to the Cr2O3 tube. The galvanic cell was lowered slowly into the hot zone of the furnace tube in order to avoid too large a thermal shock which could break the ZrO2 (CaO) crucible. The furnace was con- tinuously flushed with purified argon during the experiment. The temperature was measured with a Pt-Pt/10 pet Rh thermocouple and maintained at 1600° ± 5°C. The electromotive force was measured with a recording potentiometer. The furnace was turned off when measurements were being made in order to avoid induction effects and the reversibility of the cell was demonstrated in the usual manner. The electromotive force was measured several times over a period of approximately 1 hr. During that period the electromotive force remained constant within ± 3 pet and did not continuously drift in any one direction. After the experiment the alloys were analyzed for chromium in the usual manner. The measured electromotive forces of the cell at 1600°C, (2912°F), are listed in Table I. The activity of chromium, with solid pure chromium as the reference state, (a), was calculated using Eq. [l], , n F E I, n lna RT- U] where E is the measured electromotive force, F is the Faraday constant, and n is equal to 3, the number of equivalents per mole, (nF/RT = 18.59 volts'1 at 1600°C). The resulting activities are listed in Table I. The activity of chromium relative to pure liquid chromium was also calculated. The free energy of fusion of chromium at 1600° C was calculated using

Jan 1, 1969

By O. W. Ellis

In view of the extensive use of the brasses and bronzes in engineering practice it is indeed surprising that so little scientific work has been done on the oxides in these alloys. Recognition of the ill effects of these compounds is universally accorded, both in foundry procedure and in such specifications as cover the melting of these useful mixtures. In the latter, limits, for example, are placed on the proportions of scrap metal In the charge, and clauses governing the use of fluxes are included, the addition of fluxes to the charge being made with the object of avoiding oxidation during the process of melting and of subducing and separating non-metal-lic matter from the melt.1 In the manufacture of brass it occasionally, though rarely, occurs that the virgin metals, copper and zinc, alone arc used. In the event of virgin metals being employed, that of the higher melting point is always melted first. If it is melted under suitable conditions, little or no oxidation will occur. Whether oxidation has occurred or not, however, can best be determined by microscopic examination of a sample taken from the melt. Avoidance of Oxidation in Furnace Practice When melting virgin copper in crucible practice, the avoidance of oxidation is not difficult, nor is it hard to forestall trouble in the electric furnace. In gas-fired furnaces of the barrel type, however, the avoidance of oxidation is almost impossible, no matter what the condition of the flame, the flux employed, or the amount of charcoal included in the charge. Copper melted in furnaces of this type is almost invariably so highly oxidized as to requirc very considerable additions of such deoxi-dizers as, for example, silicon copper to render it free from cuprous oxide. As a result,, the castings produced are decidedly inferior, on account of the. large amount of silica which is engendered in the metal as a result of the reaction, Cu2O + Si = SiO2 + 2Cu. The deoxidation of such oxidized copper could, of course, be effected by means of zinc with, however, even more disastrous results.

Jan 1, 1930

By B. Ramaswami, U. F. Kocks, B. Chalmers

The latent hardening of silver and an Ag-Au alloy was investigated by lateral compression, overshoot in tension and cormpression, and the stability of multiple-slib orientations. The latent hardening of a secondary slip systenz depends on its relation to the primary slip system. For most secondary slip systems the latent hardening is larger for Ag-10 at. pct Au than for pure silver. The maximum increase in. flow stress on a secondary slip system over that of the primary slip system was 40 pct. The work hardening during the lateral-compression test on the latent system after prestress on the primary system is iuterbreted in terms of the preferential distribution of barriers to dislocation movement with respect to the active slip system in work-lzardened fcc crystals. The work-hardening in fcc crystals is mainly due to the dislocation interactions and the barriers to dislocation movement formed as a result of reactions between dislocations of different slip systems. The operation of sources on the latent system depends on the flow stress of those systems; hence, the increase in flow stress of a latent system due to glide on an active system, which is called latent hardening, is an important element in understanding the phenomenon of work hardening. The problem of latent hardening has attracted the attention of many investigators in the past. For example, a theoretical study of the elastic latent hardening of the latent systems due to glide on an operative system has been made by Haasen' and ~troh. These calculations, however, neglect the stress required for the intersection of forest dislocations by the glide dislocations, a factor which would be important for producing macroscopic strains on the secondary slip systems. The importance of this factor will become evident from the results presented here. Attempts have also been made to determine the latent hardening of different slip systems by experimental means by the methods summarized in Table I.3-9 The experimental methods used have been subject to certain limitations. For instance, in the method used by Hauser,9 frictional constraints between the specimen and the compression platen were not eliminated by proper lubrication (see Hos- ford10). Secondly, with the exception of Kocks,6 Hauser,9 and Rohm and Kochendorfer,11 latent-hardening studies have been made on only one of the slip systems, i.e., on either the conjugate or the coplanar slip system; hence, extensive results are not available on the latent hardening of different slip systems in the same materials, with the exception of aluminum.6 It was therefore decided to study the latent hardening of the conjugate, critical and half-related slip systems in silver. Similar experiments were done in Ag-10 at. pct Au to study the effect of solute (gold) on the latent hardening of silver. Lastly, indirect evidence can be obtained by a study of the orientation stability of crystals of multiple-slip orientations in tension and compression. This method has been used by Kocks6 to supplement his studies of latent hardening in aluminum. Similar studies were made at room temperature in single crystals of silver. EXPERIMENTAL PROCEDURE The single crystals of the desired orientations were grown and the tensile test specimens were prepared as described in Ref. 12. The compression tests were made on 1/4-in.-cube specimens. The specimens were cut from single crystals, in the Servomet spark-erosion machine.13 The two cut surfaces were planed using the lowest available planing rate in the machine to minimize the deformation layer. A brass strip was used as the planing tool. This method of preparation ensured plane parallel faces for the compression tests. The deformed material was removed by prolonged etching in a weak etching solution. A weak etching solution was used to prevent pitting of the surfaces and to ensure uniform etching. About 25 to 50 µ of material were removed from all faces by the etching treatment. The specimens were then annealed for 24 hr at 940°C in oxygen-free helium and cooled in the furnace to room temperature over a period of 7 hr. After annealing, the orientation of the specimens was determined by Laue back-reflection technique to make sure that no recrystallization had occurred on annealing. The compression-test technique and setup are described in Ref. 14. The Laue back-reflection technique was used to study the overshoot in tension, the overshoot in compression, and the stability of the axial orientation in tension and compression. The tests were interrupted after every few percent strain to determine the axial orientation. In investigating the overshoot in compression, the operative system was determined by studying the asterism of the Laue spots.

Jan 1, 1965

By E. W. Johnson, M. L. Hill

Cold working of iron-carbon alloys was found to increase greatly the hydrogen solubility and to decrease the diffusivity at temperatures up to 400° C. These effects are increasing functions of both the carbon content and the degree of deformation. The hydrogen behavior is consistent with the idea that cotd working creates "traps", which are concluded to be microcracks in which the hydrogen is chemisorbed. Hydrogen embrittlement is explained by the Petch theory of metal crack surface energy loss due to hydrogen adsorption. HYDROGEN embrittlement of steel has been studied for many years and has been the subject of an extensive literature, but the mechanism of the effect has not been completely understood. The embrittlement is unusual in that the ductility loss is not accompanied by an increase of the yield strength, being primarily a decrease of the fracture strength alone. The loss of fracture strength is usually most severe in the temperature range between 0°and 100°C. Here the solubility of hydrogen in the iron lattice at ordinary H2 pressures is extremely low while the diffusivity is still quite high. From the relationships between the ductility and the hydrogen content, test temperature and strain rate, it is apparent that the hydrogen atoms causing the ductility loss difbse to and concentrate in small regions of the metal which are especially susceptible to the initiation and propagation of fracture. This hydrogen segregation apparently occurs after plastic straining has begun. Below 0°C the ductility loss persists only at low strain rates in confirmation of the view that the embrittlement is diffusion .controlled. The tendency of the embrittlement to disappear above 100°C can be explained by the increasing lattice solubility of hydrogen with rising temperature. A common view of hydrogen embrittlement of steel is that the hydrogen initially dissolved in the metal lattice diffuses to structural discontinuities and there precipitates as H2 gas at very high pressures which assist the external stress in causing premature failure.1,2 The idea of a high H2 pressure in equilibrium with ordinary amounts of hydrogen in steel at room temperature is due to observations of hydrogen behavior in fully annealed material, for which the Sieverts' law constant relating solute concentration to H2 pressure is extremely small. Hydrogen-embrittled steel, however, is always plastically deformed to some extent, and therefore it is important that hydrogen embrittlement be explained primarily in terms of hydrogen behavior in plastically deformed material. Such an explanation is attempted in this paper. Previous studies of hydrogen in cold-worked steel have shown that both the solubility and the diffusion rate are significantly chaned when the steel is cold worked. Darken and Smith discovered that the amount of hydrogen absorbed from acid by cold-rolled steel at 35°C is many times greater than that absorbed by hot-rolled steel. They found also that the hydrogen permeability of the steel is unaffected by cold working. Keeler and Davis4 confirmed the high apparent solubility of hydrogen in cold-worked iron-carbon alloys at temperatures up to and even beyond the recrystallization temperature. They also found that this solubility increase accompanying cold work is a sensitive function of the carbon content, being absent when no carbon is present. The present experimental study was undertaken primarily to obtain an improved understanding of the behavior of hydrogen in cold-worked steel. Data were obtained on the effects of temperature, H, pressure, carbon content, and degree of cold work on the hydrogen solubility and diffusivity in iron-carbon alloys. These data have been helpful in elucidating the nature of the cold-worked steel structure as well as in providing information on the mechanism of hydrogen embrittlement of steel. EXPERIMENTAL Cylindrical specimens for hydrogen absorption and diffusion rate measurements were prepared from three iron-carbon binary alloys and a commercial SAE 1010 steel. The iron-carbon alloys were prepared by vacuum melting electrolytic iron with graphite in a magnesia crucible. The alloys were cast in vacuum as 2 1/2-in. sq ingots weighing about 20 lb each. The ingots were hot rolled (above 1900°F) to 5/8-in.-diam round bars and then cooled in air to room temperature. The resulting metallographic structure consisted of islands of fine pearlite surrounded by free ferrite. Chemical analyses of the materials are given in Table I. The 5/8-in. diam bars were turned to diameters such that cold reduction to the desired final specimen diameters would result in either 30 or 60 pct reduction in area (RA). The machined bars were then cold worked by swaging at room temperature

Jan 1, 1960

By Lawrence Addicks

ONE of the properties of copper, which has done much to give it its present prominent place among the useful metals, is its electrical conductivity, a property which has now become the chief criterion of 'the value of the commerical product. In pursuance of that distinctively American principle that, 1' the best is none too good," metal of the highest conductivity is usually called for even where such extreme purity is of no advantage, for instance, in the making of brass and other alloys. The average brass-founder feels nervous unless his copper is so very pure that it shows a conductivity of 99 or 100 per cent., while the character of the zinc used is usually overlooked in his anxiety. Electrolytic refining has made it possible to produce copper of a' very high degree of purity, the metallic impurities averaging but a few thousandths of 1 per cent.; oxygen, usually present in the form of cuprous oxide, bringing the total up to about a tenth of 1 per cent. The published data bearing upon the relationship between chemical purity and electrical conductivity is, however, very scant,' nearly all the work that has been done having dealt with alloys carrying considerable quantities of the foreign elements. In this paper I have brought together the results of experiments extending over a period of several years that have been carried out with the idea of determining the amount of various elements which would lower the conductivity 3 or 4 per cent.-a series of impure coppers rather than alloys. There are many precautions necessary to keep the conditions

Mar 1, 1905

By W. R. Phibbs

THE Columbia Steel Corporation, organized in 1922, and taken over by the United States Steel Corporation on Feb. l, 1930, is operating one blast furnace at Ironton, Utah, which was started on April 30, 1924, and is producing approximately 14,000 tons of pig iron per month. Half of the pig iron produced is basic iron and is used in its own plants at Pittsburg and Torrance, Cal. The ore for the blast furnace is shipped from Desert Mound, Utah, near Cedar City, in the southern part of the' State, approximately 231 miles from Iroaton. The ore is a hematite, disseminated with magnetite, the chemical analysis showing approximately 12 to 20 per cent magnetite, and under the micro- scope the ore has the appearance of a magnetite.

Jan 1, 1930

By C. E. Jr. Reistle

ALL crude oils become more viscous when chilled, but the only oils that congeal and precipitate paraffin to such an extent as actually to cause production troubles are those that contain an appreciable amount of wax. In handling these oils of high wax content, three distinct problems may be encountered before the oil reaches the refinery. The first problem is the precipitation and accumulation of paraffin in the well, either in the oil string or on the face and in the pores of the sand. The second problem is the accumulation of paraffin and the congealing of oil in the transportation lines. The third problem is the precipitation of paraffin and the formation of tank bottoms.

Jan 1, 1927