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By George Fancher, R. L. Whitting

A typical drilling mud from the Hastings oil field, Brazoria County, Texas, containing only 8 per cent (dry basis) of material of colloidal dimensions, which is largely illite, was concentrated to a density of 10.2 lb. per gal. and used in this study. The effects of water dilution, treatment with complex polyphos-phates, temperature and the time of heating upon the rheological properties of the mud were investigated. It was found that water plays an important part in chemical treatment and that sodium acid pyrophosphate and sodium tripolyphosphate were more efficient than other complex polyphosphates for chemical treatment. Muds treated with either of these chemicals manifested maximum reduction in viscosity and minimum filtration rates at low concentrations. Furthermore, .mud treated to minimum viscosity with either of these two chemicals was virtually unaffected by heat-treatment. Introduction The drilling of deep wells is dependent upon the use of drilling mud, and problems frequently arise concerning the effects on mud of temperature, prolonged heating and aging. The use of chemicals to control the rheological properties of mud is a well-established practice. Salts of weak organic acids such as sodium tannate or gallate were used at first until the complex phosphates of sodium were found to be more efficient. Consequently, it seemed important to investigate the reaction of a mud to chemical treatment with phosphates, temperature, heat-treatment and aging, particularly since previous work in the laboratory at the University of Texas had provided the particle-size distribution and mineral composition of Hastings mud. Properties or Mud Used in Experiments A large sample of the mud from a drilling well in the Hastings field, Brazoria County, Texas, was obtained directly from the circulatory system. Some of the general physical characteristics of the mud and other data are presented in Table I. Table i.—General Properties of Hustings Drilling Mud Alex- Cur-ander keet Well Well Depth when sample was taken, It.. 5720 5700 Weight. lb. per gal............... 9.5 0.8 Viscosity, sec. A.P.I.............. 47 60 Viscosity, Stormer, grams......... 80 Viscosity, centipoises............. 13 Filtration rate, c.c. per 30 min.a. . . 19.6 22.8 Salt content (chlorides), per cent... 0.13 0.12 pH............................. 8.9 8.9 The Alexander mud was used for the experimental work. Comparison with Curkeet mud indicates a considerably greater dilution but otherwise suggests similarity. The mineral composition and particle-size distribution of Curkeet mud (Table 2) are available (Fancher and Oliphant6). It is suggested that Alexander mud would have a similar composition.

Jan 1, 1943

By R. L. Whitting, George Fancher

A typical drilling mud from the Hastings oil field, Brazoria County, Texas, containing only 8 per cent (dry basis) of material of colloidal dimensions, which is largely illite, was concentrated to a density of 10.2 lb. per gal. and used in this study. The effects of water dilution, treatment with complex polyphos-phates, temperature and the time of heating upon the rheological properties of the mud were investigated. It was found that water plays an important part in chemical treatment and that sodium acid pyrophosphate and sodium tripolyphosphate were more efficient than other complex polyphosphates for chemical treatment. Muds treated with either of these chemicals manifested maximum reduction in viscosity and minimum filtration rates at low concentrations. Furthermore, .mud treated to minimum viscosity with either of these two chemicals was virtually unaffected by heat-treatment. Introduction The drilling of deep wells is dependent upon the use of drilling mud, and problems frequently arise concerning the effects on mud of temperature, prolonged heating and aging. The use of chemicals to control the rheological properties of mud is a well-established practice. Salts of weak organic acids such as sodium tannate or gallate were used at first until the complex phosphates of sodium were found to be more efficient. Consequently, it seemed important to investigate the reaction of a mud to chemical treatment with phosphates, temperature, heat-treatment and aging, particularly since previous work in the laboratory at the University of Texas had provided the particle-size distribution and mineral composition of Hastings mud. Properties or Mud Used in Experiments A large sample of the mud from a drilling well in the Hastings field, Brazoria County, Texas, was obtained directly from the circulatory system. Some of the general physical characteristics of the mud and other data are presented in Table I. Table i.—General Properties of Hustings Drilling Mud Alex- Cur-ander keet Well Well Depth when sample was taken, It.. 5720 5700 Weight. lb. per gal............... 9.5 0.8 Viscosity, sec. A.P.I.............. 47 60 Viscosity, Stormer, grams......... 80 Viscosity, centipoises............. 13 Filtration rate, c.c. per 30 min.a. . . 19.6 22.8 Salt content (chlorides), per cent... 0.13 0.12 pH............................. 8.9 8.9 The Alexander mud was used for the experimental work. Comparison with Curkeet mud indicates a considerably greater dilution but otherwise suggests similarity. The mineral composition and particle-size distribution of Curkeet mud (Table 2) are available (Fancher and Oliphant6). It is suggested that Alexander mud would have a similar composition.

Jan 1, 1943

By J. R. Long, T. R. Graham, R. G. Feustel, R. S. Dean

THE comprehensive study of the copper-manganese-zinc alloy system in the Bureau of Mines Laboratories has so far been principally concerned with alloys that lie within the alpha solid solution field of the system. Two regions, one centering about 65 per cent copper, 10 manganese and 25 zinc, and the other centering about 70 per cent copper, 20 manganese, 10 zinc, have been carefully examined.1,2 These have indicated that when the alloys are made with electrolytic manganese considerable amounts may be readily introduced and that the strength and hardness are increased without excessive losses in ductility. In the course of the work of establishing the limits of the alpha solid solution range,3 enough of certain of the alloys was prepared to permit determination of their physical properties at a future date. The 60 per cent copper alloys concerned here are part of that series. They cross through the alpha field and into the adjacent alpha plus beta and alpha plus X fields, and are of interest because they offer some information on the effects of manganese on alloys lying in these fields. COMPOSITION AND FABRICATION OF ALLOYS The chemical composition of the alloys involved is given in Table I. They were intended to contain 60 per cent copper with manganese increasing from 5 to 25 per cent in 5 per cent steps and zinc decreasing [ ] from 35 to 15 per cent. The analyses are so close to the intended composition that the alloys will be referred to hereafter by their nominal compositions. They were finished into sheet by cold-rolling and intermediate annealing procedures calculated to produce sheet 1/16 in. thick, cold-reduced by 20, 40, 60, and 80 per cent in thickness. Physical properties were determined on standard flat tensile specimens with 4-in. gauge length, although the test gauge section used was 2 in. The properties were obtained on cold-worked material and on material annealed at temperatures ranging from l00° to 1500°F. after 60 per cent cold reduction. Since an annealing temperature of 1200°F.

Jan 1, 1946

By Reynold Q. Shotts

CHEMICAL methods, based on the relative rates of oxidation of fusain, bright coal, and dull coal by nitric acid, have been devised to determine these coal components.1-4 Results obtained by oxidation methods for fusain have been checked against results obtained from microscopic methods5, 6on duplicate samples of the same coals, but to the author's knowledge this has not been done for bright and dull coal components. For this reason it is not certain that the two methods of analysis identify essentially the same chemical or physical units. It would be highly desirable to see results of the application of both methods to duplicate samples, but in the absence of any such data the author has attacked the problem indirectly. From the U. S. Bureau of Mines samples were obtained of three Alabama coals which the USBM had analyzed optically and reported on over the past 30 years. These samples were subjected to analyses by oxidation rate methods. Results of this work, and comparisons with the USBM analyses, have been published." This was the first indirect approach to the problem. The present report attempts a second indirect approach by way of internal validation. By nitric oxidation samples of two whole coals were carefully analyzed for fusain, bright coal, and dull coal. One coal was analyzed in duplicate. Duplicate portions of each of the coals were divided into three density fractions by means of heavy liquids. A duplicate portion of one of the coals was divided by sieving into three size fractions. Each fraction was analyzed by oxidation and its percentage composition calculated in terms of fusain, bright coal, and dull coal. Because the weight percent of each fraction was known, a material balance calculation for the whole coal was also made. The resulting reconstituted analysis of the whole coal could be compared to that determined by direct analysis. In addition, specific reaction rate constants were determined for each component and for each whole coal or fraction. Arbitrary reactivity indexes were calculated by dividing by 100 the sum of the products of the percent of each component in the coal and its specific reaction rate constant. The resulting figure was an average reactivity index for each coal or fraction. Weighting the reactivity indexes for each fraction by the percent of the fraction in the coal gave a reactivity index for each whole coal which could be compared to that calculated directly from the whole coal analysis. If oxidation analyses really delineate definite physical entities within the coal, or even definite groups of similar entities, reconstituted analyses calculated from fraction analyses should check closely those made of the whole coal. It probably is true that optical methods identify and describe a greater variety of components than do chemical methods and that variations are wide in the appearance and quantity of those components identified optically. Chemical methods based upon differences in oxidation reaction rates would of necessity be less discriminating, as between similar components, than would optical methods. The procedures followed for oxidizing the samples, analyzing the residues, plotting and calculating the percentage of each component, and calculating its specific reaction rate constant have been fully described.'-' In brief the method originally proposed by Fuchs et al.1 for the determination of fusain consists of the oxidation of small samples of coal in boiling 8N nitric acid in a condenser-fitted flask. After boiling for periods of 1/2 to 4 hr, the unoxidized residue is filtered and washed. The washed residue is treated with normal sodium hydroxide, diluted, and allowed to stand for several hours. The resulting brown liquor is removed, and the filtered residue dried, weighed, ignited, and weighed again. The ash-free residue is expressed as a percent of original dry, ash-free coal. The percent residue is plotted against time, and the extrapolation of this line to zero time gives the percentage of dry ash-free fusain present in the original sample. The shape of the resulting time plots has been explained' by the assumption that they are the result of two different types of reaction, the first part representing a first order reaction with rate a func-

Jan 1, 1956

By David Baker

When the skip-hoist was first tried as a means of filling the blast-furnace it made a great many enemies and very few friends among furnace managers. This state of affairs continued until the Duquesne furnaces were built, which demonstrated not only the possibilities of a furnace-stack in the way of production, but also the ability of the skip-hoist to charge the materials necessary to produce the large tonnlage obtained. Every furnace manager, who has operated stacks fitted with the vertical hoist and the hand-barrow system of filling, remembers that the momentous question about the furnace, particularly during a good run, was: "Are you keeping her full ?" and many a good run has been spoiled by the furnace " getting away from the men." With the new birth of the skip-hoist this trouble was eliminated ; but alas! Other and more important difficulties arose. The distribution of the stock, the importance of which is never learned until many different ores and fuels have been tried, demanded closer attention. With all the defects of the hand-barrow system, the distribution—When the top fillers were conscientious in carrying out the scheme of filling arranged after thoughtful consideration by the manager—mas above criticism. It is said that the modern skip-hoist, equipped with an elliptical hopper and receiving-cylinder, and discharging over a small bell into the main hopper, will give just as good results as those obtained with hand-barrow charging, but I cannot agree with this statement. I grant, that under very favorable conditions, the mechanical furnace-top will do apparently as well as the

Jan 1, 1905

By P. Barnes

(Read at the Amenia Meeting, October, 1877.) THE subdivisions of this account are numbered 27, 28, 29, 30, 31, 32, and 33, in the general series of construction accounts, and give the details of cost of the various items of the work, as noted below: Accounts 32 and 33 -relate to hand-tools and to heaters, and, being quite small in total amount, are omitted in this statement.

Jan 1, 1878

By K. Osseo-Asare

The thermodynamics of solid-aqueous solution equilibria up to 200°C In the systems Me-NH3 H2 0 (Me=Cu, Ni, Co) are summarized with predominance area diagrams generated with the DIAGRAM computer program. The implications of the diagrams to ammonia hydrometallurgy are discussed.

Jan 1, 1981

By Persifor Frazer

Among the geological problems with wliicli the present PenufiyI vanirr Geological Survey has had to deal is the relative age of wries of atrata passing around and through the city of' Philadelphia, Bucks, Chester, and Delaware counties. Rogers includes all these roclrs in 11is hypc~zoic series, and every student, so far as the writer knows, with one exception, has assigned to them a position beneath the Pobdam sandstone, or Primal" of that eminent and gifted geologist. So far as regards the srllall portions of this belt, to which it is the intention of the present paper to draw attention, even the oiie geolo-

Jan 1, 1881

By R. E. Allen

ONE of the most unusual oil field engineering accomplishments of the past two years is the development and rapid advance in the directed drilling of wells. Directed drilling as referred to herein is the controlled steering of the drill stem in the required direction to a given location in the oil sand. The deliberate drifting of holes is an act so far removed from what has been considered good drilling practice that all of the old questions of correlation, drillability and production difficulties are revived. Only a few years ago, during the boom days of Seminole and Santa Fe Springs, the crooked-hole problem, as it was then called, occupied a primary position among the topics of the day in the fields of California and the Mid-Continent. The net result of all the discussion and study at that time was the conclusion that oil wells should be drilled with as little deviation from

Jan 1, 1933

By Smith, George Otis

THE matter that I have on my mind this evening is engineering's need of an open forum. Our fathers of three centuries ago were pro-testanta for freedom of speech and thought in matters religious; later, our fathers were revolutionists for freedom of speech in matters political; until today freedom of speech has become so universal throughout the land that even in the sanctuary of our homes, at times, we have to turn off the loud-speaker. Talk is not always a condition of progress, but light is everywhere necessary to growth, whether the growing thing is a blade of grass, a baby chick, or a young idea, and we must regret anything that tends to shut out the light from the operations of business and industry. Of course, I realize there is little that is novel in what I am saying. Indeed, I have found that Dr. James Douglas-a name we love to honor in our Institute-as long ago as 1907, gave an address at the Toronto meeting that any of us would be proud to be author of twenty-one years after. Dr. Douglas at that time spoke on secrecy in the arts and the text then taken by this leader in metallurgical technique and in the constructive management of big business was "the dangerous temptation to adopt secretive methods by very large corporations." In both thought and language Dr. Douglas was direct and vigorous and he needs no internreter. He advocated the wide open door for ideas on two counts: advancement of technical knowledge and education of public opinion. A few sentences will serve not only to prove the vision of James Douglas, but also, I hope, tempt you to hunt up his address in the Institute's TRANSACTIONS, and thus get his whole thought first hand.

Jan 1, 1928

By L. D. Hall, S. J. Rothman

DIFFUSION coefficients of RaD (PD) and RaE (Bi) in a Bi-0.255 atomic pct Pb alloy have been measured by the methods outlined in a previous paper.' The following changes were made in the experimental procedures: the bath was made up of about 400 to 500 g Bi; and no correction was made for the volume change of bismuth on melting. The data are presented in Table I and Fig. 1. A least-squares analysis of the data yielded D = (0.120 t 0.09) exp ( -9680 + 1070/RT) D- (0.0465 0.001) exp (-8100 + 466/RT). Statistical analysis of the data indicated that the activation energies are significantly different at the 50 pct level, but not at the 75 pct level, while the D values are significantly different at the 97.5 pct level, but not at the 99 pct level. The differences are thus not as clear-cut as they were for lead. However, bismuth diffuses faster than lead in high bismuth alloys as well as in lead. The high activation energies, more than twice the value calculated from viscosities, are in good agreement with the results of Grace and Derge.' No data were obtained at higher temperatures because of gas bubble formation in the capillary. Acknowledgments This work was supported by the Office of Ordinance Research under contract DA-04-200-ORD-178. The authors thank 0. P. Vieria and M. Volpe for help in the experimental work.

Jan 1, 1957

By Eugene P. Pfleider, Claus Freyberger

Generally, the different methods of financing new mining projects are not well understood by the engineers and supervisory personnel. Nor are the effects of these alternatives on depletion, taxes and profitability readily apparent to even the sophisticated management personnel without the aid of cash flow studies. Fortunately, with the advent of the computer it is possible now to simulate many different combinations of 1) equity, 2) loan and 3) production payment financing with little effort. A general computer program for cash flow analysis of mining ventures has been developed and applied as a case example to a 1967 feasibility study of the Underground Mining of Minnesota Taconite. The effects on profitability as measured both in rates-of-return and present value are presented for various financing combinations. In addition, percentage depletion rates were altered so as to measure the impact of this statuatory allowance. Based on the cost data as presented in the aforementioned 1967 feasibility study, and assuming 7% loans, the rates-of-return vary from 9. 9% to [00] % on equity variations and from 9. 9% to 11.4% on total invested funds.

Jan 1, 1969

February 20th, 1872. THE Institute assembled on Tuesday evening, in the building of the University of Pennsylvania. In the absence of President Thomas, Vice-President Raymond occupied the chair. The Institute was welcomed in an eloquent and thoughtful address by Prof. J. P. Lesley, to which Mr. Raymond responded. Invitations were announced from the proprietors of Sellers' Tool Works, Whitney's Car-wheel Works, the Baldwin Locomotive Works, Lewis & Brothers' White Lead Works, the Southwark Foundry, Harrison's Boiler Factory, the University of Pennsylvania, and the Academy of Natural Sciences. The following gentlemen, being duly recommended by the Council as members and associates, were unanimously elected Alexander, John S., - Philadelphia, Pa. Biddle, E. R., - New York. Britton, J.. Blodget, - Philadelphia, Pa. Brooks, Maj. T. B., - Marquette, Mich. Brown, D. P., - Pottsville, Pa. Canfield, Edw., - Dover, N. J. Cogswell, W. B., - Franklin IronW'ks, N.Y. Cornwall, Prof. H. B., - New York. Edwards, Daniel, - Danville, Pa. Estabrook, John D., - Philadelphia, Pa. Firmstone, William, - Easton, Pa. Fritz, John, - Bethlehem, Pa. Gignoux, Charles, - New York. Grant, E. M., - Tuskegee, Ala. Humphreys, A. W., - New York. Ingham, W. A., - Philadelphia, Pa. Keyes, W. S., - Eureka, Nev. Kimball, Dr. J. P., - New York. Law, Charles, - Pittston, Pa. Neilson, W. G., - Philadelphia, Pa. Newberry, Prof. J. S., - New York. Pearse, John B, - Steel Works P. O., Pa. Ricketts, P. De P., - New York. Scranton, Col. Charles, - Oxford, N. J. Sontag, Hugo, - Cologne, Prussia. Steele, Thomas C. - Summit, Pa. Wharton, Joseph, - Philadelphia, Pa.

Jan 1, 1873

By G. Sachs, G. Espey

It is well known that high residual stresses are created in tubing by the sinking process, in which no internal tool or mandrel is used.l-4 In this process, the wall thickness is usually slightly increased.4,5 In tube drawing with a plug, the residual stresses are gradually reduced with increasing reduction of wall, and, by the conventional approximation methods of stress measurement, no stress is detected in tubing in which the wall reduction is over 50 per cent of the total reduction in cross-sectional area.l,6 It has also been observed that higher stresses are set up by the use of wide-angle dies than by acute dies.? 'he actual stress distribution in drawn tubing has been investigated by a few workers,7"9 but has not been related to the conditions of the drawing process. Some attempts have been made to correlate accelerated cracking tests for stresses in brass products with the magnitude of the circumferential stresses and the condition of the metal. l-10 Materials and Preparation The material used in this experiment was commercial cartridge-brass (70 per cent Cu, 30 per cent Zn) tubing in the straightened and annealed condition.† This tubing was of various outside diameters and had a wall thickness of 0.032 in. It was sunk to 1/2-in. outside diameter by means of an experimental 10,000-lb. hydraulic draw-bench, with a maximum drawing speed of 8 ft. per minute. All dies were of 1/2-in. diameter. Various die materials and contours were used in order to study the effect of die design on residual stresses in the tubing; the specifications for the dies are given in Fig. I. Castor oil was used throughout as lubricant. Chattering occurred in sinking some of the tubing, particularly when dies having the more acute angles were used, but the tubes showing chatter marks did not differ markedly from those with a smooth surface regarding the magnitude of residual stress. The source of the chattering has not yet been revealed. The wall of the tubing becomes thicker during s nking, as previously observed.4,5 The increases in wall thickness were 3, 7 and 9.5 per cent on the average for 6, 20 and 33 per cent reductions in diameter, no effect of the contour being noticeable. The reductions mentioned throughout this investigation do not consider this fact, but are reductions of the outside diameter. For the evaluation of the residual stress two fundamentally different methods were used. The approximation methodl,ll of splitting a certain length of tubing was employed to obtain a bird's-eye view of the effect of various drawing conditions on the circumferential stress measured by the diameter change occurring On splitting. For

Jan 1, 1942

By G. Sachs, G. Espey

It is well known that high residual stresses are created in tubing by the sinking process, in which no internal tool or mandrel is used.l-4 In this process, the wall thickness is usually slightly increased.4,5 In tube drawing with a plug, the residual stresses are gradually reduced with increasing reduction of wall, and, by the conventional approximation methods of stress measurement, no stress is detected in tubing in which the wall reduction is over 50 per cent of the total reduction in cross-sectional area.l,6 It has also been observed that higher stresses are set up by the use of wide-angle dies than by acute dies.? 'he actual stress distribution in drawn tubing has been investigated by a few workers,7"9 but has not been related to the conditions of the drawing process. Some attempts have been made to correlate accelerated cracking tests for stresses in brass products with the magnitude of the circumferential stresses and the condition of the metal. l-10 Materials and Preparation The material used in this experiment was commercial cartridge-brass (70 per cent Cu, 30 per cent Zn) tubing in the straightened and annealed condition.† This tubing was of various outside diameters and had a wall thickness of 0.032 in. It was sunk to 1/2-in. outside diameter by means of an experimental 10,000-lb. hydraulic draw-bench, with a maximum drawing speed of 8 ft. per minute. All dies were of 1/2-in. diameter. Various die materials and contours were used in order to study the effect of die design on residual stresses in the tubing; the specifications for the dies are given in Fig. I. Castor oil was used throughout as lubricant. Chattering occurred in sinking some of the tubing, particularly when dies having the more acute angles were used, but the tubes showing chatter marks did not differ markedly from those with a smooth surface regarding the magnitude of residual stress. The source of the chattering has not yet been revealed. The wall of the tubing becomes thicker during s nking, as previously observed.4,5 The increases in wall thickness were 3, 7 and 9.5 per cent on the average for 6, 20 and 33 per cent reductions in diameter, no effect of the contour being noticeable. The reductions mentioned throughout this investigation do not consider this fact, but are reductions of the outside diameter. For the evaluation of the residual stress two fundamentally different methods were used. The approximation methodl,ll of splitting a certain length of tubing was employed to obtain a bird's-eye view of the effect of various drawing conditions on the circumferential stress measured by the diameter change occurring On splitting. For

Jan 1, 1942

By Alan U. Seybolt

In examination of some cold-rolled copper and cupronickel that contained a little columbium, it was discovered that these alloys were unusually resistant to annealing. This effect was suficiently pronounced to warrant some investigation of the annealing characteristics of such compositions. Experimental Procedure The alloys were made from cathode copper, electrolytic nickel, and a special copper-columbium hardener alloy furnished by the Electro Metallurgical Corporation. This hardener alloy contained 10 per cent columbium, with tantalum, aluminum and iron as major impurities. The melting was carried out in a clay-graphite crucible in a high-frequency induction furnace! under a charcoal or electrode carbon cover. No deoxidizing additions were made. The 7-lb. copper heats were poured into a steel mold, hot-rolled to 1/4-in. thickness, and annealed for 56 hr. at 760°C.; the cupronickels were annealed I hr. at 815°C. The material was then cold-rolled to a 50 per cent reduction in thickness and annealing tests were carried out on this 1/8-in. hard-rolled strip. A little silver was added to copper-columbium alloys 402 and 403 to find out

Jan 1, 1942

By Alan U. Seybolt

In examination of some cold-rolled copper and cupronickel that contained a little columbium, it was discovered that these alloys were unusually resistant to annealing. This effect was suficiently pronounced to warrant some investigation of the annealing characteristics of such compositions. Experimental Procedure The alloys were made from cathode copper, electrolytic nickel, and a special copper-columbium hardener alloy furnished by the Electro Metallurgical Corporation. This hardener alloy contained 10 per cent columbium, with tantalum, aluminum and iron as major impurities. The melting was carried out in a clay-graphite crucible in a high-frequency induction furnace! under a charcoal or electrode carbon cover. No deoxidizing additions were made. The 7-lb. copper heats were poured into a steel mold, hot-rolled to 1/4-in. thickness, and annealed for 56 hr. at 760°C.; the cupronickels were annealed I hr. at 815°C. The material was then cold-rolled to a 50 per cent reduction in thickness and annealing tests were carried out on this 1/8-in. hard-rolled strip. A little silver was added to copper-columbium alloys 402 and 403 to find out

Jan 1, 1942

By Avnulf Muan, Egil Aukrust

The activity-composition curve for cobalt oxide in (Co,Fe)304 solid solutions with spinel-type stmcture has been determined experimentally by studying the equilibrium between the spinel phase and a coexisting cobaltowüstite phase, "(Co,Fe)O", at 1200°C. A large negative deviation from ideal behavior prevails in the spinel at low cobalt oxide concentrations and a positive deviation at high cobalt oxide concentrations. The activity-composition curve for iron oxide in the solid solution is determined from the above curve by integvation of the Gibbs-Duhem equation along the join Co3O4,-Fe3O4. The standard free energy of formation of cobalt ferrite, CoFe2O4, from the oxide components CoO and Fe2O3 is calculated to be -8.2 kcal. ThERMODYNAMIC properties of (CO,Mn)3O4 solid solutions with spinel-type structure have been presented recently.' The present paper deals with similar relations in another spinel solid-solution phase, that represented by the system Co3O4-Fe3O4. The principles involved in measurements and calculations of thermodynamic properties for the system Co3O4-Fe3O4 are analogous to those used and discussed in detail in the work on (CO,Mn)3O4. A (CO,Fe)3O4 solid solution coexists in equilibrium with a (Co.Fe)Ot solid solution over a considerable Here acOo1.33 and aao are the activities of cobalt oxide in the spinel and the oxide solid solutions, respectively, pO2, is the oxygen pressure of equilibration, and pb, is the oxygen pressure at which CoO and CosO4 coexist in equilibrium in the binary system Co-O at the same temperature. The activity-com position curve for cobalt oxide in the (Co,Fe)O solid solution in contact with metal has been determined in a previous investigation by the present authors.' The system shows a small positive deviation from linear behavior. Because of the large defect concentration in wiistite and in (Co,Fe)O solid solutions, one cannot assume that the activity-composition relations in the oxide phase coexisting with a spinel phase at relatively high oxygen pressures are the same as those prevailing in the oxide solid solution coexisting with metal. However, a Gibbs-Duhem integration over the ternary Co-Fe-0 solution can be used to determine activities of cobalt and iron, and hence of CoO and FeO, from a knowledge of the oxygen potentials. Several papers have dealt with the subject of application of the Gibbs-Duhem equation to multi-component systems. 3-6 In the present case, it was

Jan 1, 1964

By Alan U. Seybolt

IN examination of some cold-rolled copper and cupronickel that contained a little columbium, it was discovered that these alloys were unusually resistant to annealing. This effect was sufficiently pronounced to warrant some investigation [ ] of the annealing characteristics of such compositions. EXPERIMENTAL PROCEDURE The alloys were made from cathode copper, electrolytic nickel, and a special copper-columbium hardener alloy furnished by the Electro Metallurgical Corporation. This hardener alloy contained 10 per cent columbium, with tantalum, aluminum and iron as major impurities. The melting was carried out in a clay-graphite crucible in a high-frequency induction furnace, under a charcoal or [ ] electrode carbon cover. No deoxidizing additions were made. The 7-lb. copper heats were poured into a steel mold, hot-rolled to ¼ -in. thickness, and annealed for ½ hr. at 760°C.; the cupronickels were annealed I hr. at 815°C. The material was then cold-rolled to a go per cent reduction in thickness and annealing tests were carried out on this 1/8-in. hard-rolled strip. A little silver was added to copper-columbium alloys 402 and 403 to find out

Jan 1, 1941

By Michael Tenebaum, C. C. Brown

In recent years, the importance of slag control in basic open-hearth operations has been universally recognized. To effect such control during the working period of the heat, methods have been developed to measure or estimate slag oxidation and slag basicity. While satisfactory rapid chemical methods have been developed to determine slag oxidation, no completely adequate method of evaluating basicity has yet been provided. The most generally accepted control methods of measuring slag basicity are based on visual cstimates. While considerable benefit may be derived from such estimates, the need for some measurable indication of slag basicity has become increasingly apparent. In a recent paper, Philbrook and Jolly suggested a promising technique for making the basicity determination. Their method consists of measuring the pH of a mixture of powdered open-hearth slag and distilled water. It was found that a relation could be established between the slag basicity and the alkalinity of the water mixture as measured by the hydrogen-ion concentration. The general procedure followed in making the measurements and the considerations involved in constructing the original curves are given in the paper of Philbrook and Jolly and need not be repeated. It is the purpose of this paper to discuss some of the factors considered in applying the pH measurements to actual slag control and to present some of the results of its apphcation. Factors Involved in Measuring pH of Water-slag Mixtures To facilitate the application of the pH control system, it was desirable that no alteration be made in the routine methods of sampling and crushing the furnace slag. Some of the factors considered before establishing a curve to relate slag basicity with the pH reading arc reviewed individually in the following paragraphs. Effect of Cooling Rate Under actual operating conditions there can be considerable variation in the temperature of the piece of slag crushed for the pH determination. To determine whether variations in crushing temperature or in cooling rate would affect the pH reading, a series of four samples was prepared from each of two separate slags. These samples represented conditions far more extreme than would actually be encountered. To obtain these samples, a thick pancake of slag was poured. One piece of this pancake was crushed immediately after it had solidified. Another piece was water-quenched and then crushed. A third piece was allowed to air-cool to room temperature before crushing. The fourth sample was prepared from a chilled slag. This sample was poured onto a heavy inclined steel plate at the

Jan 1, 1945