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THE Nominating Committee appointed at the Division meeting in October and consisting of Frank A. Herald, A. W. Peake, C. R. McCollom, Joseph Jensen, H. W. Camp, C. P. Watson, F. Julius Fohs, George Otis Smith, J. B. Umpleby, J. M. Lovejoy and A. W. Ambrose, have presented the following ticket for the year 1929: Chairman, Joseph B. Umpleby; associate chairman, A. C. Rubel; secretary-treasurer, R. Van A. Mills; vice-chairman for Economics, Warren A.. Sinshein~er; vice-chairman for Engineering Education, H. C. George; vice-chairman for Engineering Research, Harry H. Hill; vice-chairman for Production, C. P. Watson;vice-chairman for Refinery Engineering, A. D. David. For Production Engineering Charles V. Millikan. is named vicechairman, with ,Charles E. Beecher, Glenn D. Robertson and W. W. Scott as associate vice-chairmen. The Executive Committee named is to consist of Joseph B. Umpleby, chairman with A. W. Ambrose, Charles E. Beecher, A. D. David, Glenn D. Robertson, H. C. George, Harry H. Hill, John M. Lovejoy, Charles V. Millikan, R. Van A. Mills, Earl Oliver, A. W. Peake, A. C. Rubel, W. W. Scott, Warren A. Sinsheimer and .C. P. Watson, members. Ballots will be mailed to members of the Division.

Jan 1, 1928

By Emil Gathmann

STEEL as it is poured, or teemed, into the mold for forming the ingot may be broadly separated into two divisions; i.e., effervescing or gassy steel, also termed evolution steel, and non-effervescing or killed steel, also termed solution steel. Between these primary divisions there are various types having the characteristics of both divisions but really not belonging to either; such steels are termed semi-piping, rising, or wild, as the type may be. True unkilled, or effervescing, steel should contain large volumes of gases, which are evolved while the metal is being teemed, or cast from the ladle nozzle into the mold, and while the temperature of the steel is being reduced prior to the solidification or freezing of the steel, the upper portion, or top, of the ingot remaining liquid due to the evolution of gases until an ingot skin of considerable thickness has been formed. These gases consist principally of hydrogen, carbon monoxide, nitrogen, and ammonia. It is generally understood that nitrogen gases are the first evolved and form the skin blowholes, at times troublesome, in the forming solidifying ingot. Ingots made of effervescing steel will always contain a large number of blowholes. Such blowholes are not deemed objectionable in various products if they occur well within the interior of the ingot where they will not be subject to oxidation upon the ingot's cooling and subsequent re-heating and rolling or forging. Very little top or bottom discard is taken from this type of ingot as pipes, or large shrinkage cavities, at the upper portion of the ingot do not usually occur, the difference in volume between the liquid and the solid steel (6 to 10 per cent.) being compensated for by the innumerable blowholes distributed throughout the body of the , ingot. Of the 40,000,000 tons of steel made in the United States during the year 1919, at least 35,000,000 tons of ingots were made of gassy or semi-gassy steel. Killed, or solution, steel is termed true piping steel from the characteristic pipe or shrinkage cavity that usually occurs in the uppermost central portion of the ingot.

Jan 8, 1920

By Rodolfo V. de la Cruz, Richard E. Goodman

Knowledge of the initial state of stress in rocks provides a key to the solution of many problems in rock mechanics. The initial state of stress is part of the basic data required for rational design of structures in rock, since its redistribution when engineering activities are conducted is a primary load on the rock portion of the engineering system. Knowledge of initial and subsequent changes in the state of stress is also relevant in the study of active faults and crustal strain. The purposes of stress measurements are not generally well served by methods which disclose only one of the stress components at a point. Recently, interest has centered on overcoring methods which though ex- pensive and difficult have the important advantage of yielding data on three or more stress components. In a previous paper, the authors introduced a new method-termed borehole deepening-based on measurement of the deformations that occur close to the bottom of a borehole when it is deepened by further drilling without overcoring.l The proposed method is at a disadvantage when compared with over- coring procedures in that the quantities to be measured are somewhat smaller and the measuring environment is more hostile. However, the borehole deepening method presents three distinct advantages in comparison with overcoring procedures: (1) Using the same borehole, both the initial and the subsequent changes in the state of stress can be obtained by borehole deepening. Stress changes with time are

Jan 1, 1970

By Arthur Taggart

SOME years ago, A. M. Gaudin and one of the authors published a paper showing removal of tar acids from solution by sulfides preferentially as compared to gangues (specifically by galena as compared to quartz).1 The underlying phenomenon was classed as adsorption, and the paper went on to develop the general thesis that so far as water-soluble frothing and collecting agents in flotation are concerned, the phenomenon of adsorption is one of controlling importance. Adsorption was defined in that paper as "a process of rearrangement of a system, which results in establishing a difference in concentration, as between the interfacial layers and the bulk of the phases, of a substance or substances initially uniformly dispersed in one or several of the phases." The paper went on to develop the relation between adsorption and surface energy according to Gibbs' equation (which may be thrown into the form U/c = KdT/dc, where U = excess concentration in surface layer, c = concentration, T = surface tension, and K is a constant), and pointed out that, according to this equation, degree of adsorption and change in surface tension vary directly. The present paper offers a somewhat different definition for the term adsorption; and sets up, in sweeping terms, the generalization that simple chemical reaction underlies the functioning of the flotation reagents which control mineral collection, when these reagents are soluble in and act from solution in the water of the pulp.

Jan 1, 1930

By William P. Roe, James F. Ellis, W. P. Fishel

This paper reports the distribution of sulphur between iron and titanium in Fe-Ti-S alloys and in Fe-Ti-C-S alloys. The compound TiS was found, which exists as a separate phase at temperatures below 1200°C. Titanium in steels reacts with sulphur in preference to carbon. THE general relationship between sulphides and oxides suggests that titanium should form a sulphide having properties similar to those of titanium oxide. Specifically, titanium should form a sulphide having a high melting point, indicating a stable compound of low solubility in iron. In order for titanium to function as a desulphurizer or sulphur-fixing agent, it must form a stable sulphide. In order for titanium to be useful in steels as a sulphur-fixing agent, it must react with sulphur in preference to carbon; and to prevent red shortness, the sulphide formed must have solubility characteristics such that grain-boundary precipitation of a low melting phase be prevented. The terms desulphurizer and sulphur-fixing agent when used in this paper mean that titanium effectively ties up the sulphur as a stable sulphide of titanium and prevents the formation of FeS. The partition of sulphur between iron and titanium was studied first in a series of Fe-Ti-S alloys with carbon absent, and then in similar alloys with carbon present. It has been established1 a that titanium forms in Fe-Ti-S alloys a sulphide of undetermined composition which can be identified microscopically, and that the titanium-sulphur compound does not respond to sulphur printing. It has been suggested" that titanium acts as a sulphur-fixing agent, although little proof has been given. A report% f The Advisory Committee on Metals and Minerals summarizes the existing knowledge concerning substitutes for manganese in steels. Distribution of Sulphur Between lron and Titanium with Carbon Absent The alloys for this investigation were made by -melting Armco iron, metallic titanium, and iron sulphide in alundum crucibles in an induction furnace. The titanium was added after the other ingredients had melted. In these alloys it is recognized that some TiO, is present, since the melts were made in the air and since no other deoxidizing agent was used; therefore, some of the titanium was not available for union with sulphur. Thirteen ingots were made. Ingots 2 to 8 were cast in baked-sand molds; ingots 12 and 13 were cast in metal molds; and ingot 9 was allowed to cool in the crucible in which it was melted. All ingots were annealed at 900°C for 3 hr and were cooled slowly in the furnace. Subsequent information indicates that this anneal had no effect upon the titanium sulphide particle size, since the sulphide does not go into solution at this temperature. The ingots as-cast were approximately 8 in. long and % in. diam. The compositions of the eight ingots and the results of the partition of sulphur are recorded in Table I. Total titanium and total sulphur were determined by standard gravimetric methods. Sulphur, as iron sulphide, was determined by the evolution method. Boiling HC1 (1:4) liberates the sulphur from iron sulphide, but leaves the titanium sulphide practically undecomposed. A complete separation of titanium sulphide and iron sulphide cannot be made by digesting these compounds in dilute HC1 since titanium sulphide was found to dissolve slowly. The amount of titanium sulphide decomposed will depend upon the time in contact with the acid and upon the particle size of the sulphide. The point

Jan 1, 1952

By F. Selig, A. S. Odeh

A second-order approximation to the exact solution of the diffusivity equation corresponding to the pressure build-up of a well producing at a variable rate is derived. This approximation is applicable when the well's shut-in time is larger than the total time elapsed since the well was first produced. The resulting equations are compact in form and easy to use. Thus, the need for Horner's' theoretically precise but rather laborious solution to the above problem is eliminated. In addition, these equations apply where the use of Horner's widely known approximate method is questionable. From a practical point of view, the reported method is best suited for analysis of drill-stem tests and short production tests conducted on new wells. INTRODUCTION The utility of drill-stem and short production tests in reservoir studies has long been recognized by the reservoir engineer. If interpreted correctly they could lead to a wealth of information upon which may depend the success or failure of reservoirs' analyses. Initial reservoir pressure and the average flow capacity are two quantities that are normally sought from a drill-stem and/or a short production test analysis. Pressures are the most valuable and useful data in reservoir engineering. Directly or indirectly, they enter into all phases of reservoir engineering calculations. Therefore, their accurate determination is of utmost importance. The flow capacity kh of the reservoir is indicative of its commercial capability. In addition, it can indicate the presence of a darnaged zone around the wellbore and, thus, the necessity for remedial measures. Of the several methods used to analyze drill-stem and short production tests, Horner's' method is by and large the most common. It applies to an infinite reservoir and or a limited reservoir where the effect of production has not been felt by the boundary. Horner's method makes use of the so-called "point-source" solution of the diffusivity equation. The point-source solution is approximated by a logarithmic function and the superposition theorem is utilized to give the familiar pressure build-up equation where is the shut-in time, q is in reservoir barrels per day and the rest of the symbols conform with AIME nomenclature. Eq. 1 was derived for a well which produced at a constant rate q from time zero to time t and was then shut in. In actuality, such a constant rate of production does not normally obtain. Therefore, a correction must be applied to Eq. 1 to account for the varying rates of production. Horner suggested two methods. The first, which results in a theoretically accurate solution, is rather lengthy and laborious and, thus, it is not suited for routine analysis. The second which has been termed a "good working approximation" is the one used by the majority of the reservoir engineers. In the second method, Eq. 1 is modified by simply introducing a corrected time t, and writing where q is the last established production rate prior to shut-in, and t, is obtained by dividing the total cumulative production by the last established rate. Horner's original paper does not give any indication that this method of correction is based on any theoretical justification. In addition, there is a question as to what constitutes the last established rate. In case of a drill-stem test some engineers use the average rate obtained by dividing the total fluid produced by the total flow time, while others calculate the average rate by dividing the total fluid produced by the last flow-period time. Obviously, different results obtain for the different flow rates used. Because of this, a simple method to the varying-rate case was developed which is theoretically sound and which defines clearly the flow rate and its associated time to be used in the calculations. The final equation arrived at is where q* and t* are a modified rate and time, respectively, and can be easily calculated. In addition, it is shown theoretically that Horner's approximate method, if used for a variable-rate case, gives the correct pressure but would not be expected to give the correct flow capacity. MATHEMATICAL ANALYSIS The general equation governing the flow of slightly compressible fluid in porous media may be written as The elementary solution to Eq. 4, representing an instantaneous withdrawal of Q units volume of fluid at the origin at t = 0, is known as the instantaneous sink

By C. W. Spencer, F. N. Rhines, R. J. Knight

Ametallographic study has been made of the peritectoid transformation as it occurs in two Ag-A1 alloys, containing 6.0 and 6.9 wt pct Al, respectively. After equilibrating at 475°C, these alloys were transformed isothermally just below the peritectoid temperature which lies at about 450°C.1-3 Peritectoid transformation in this alloy system consists in the reaction of a and 5 to form µ. The crystal structures of the a, µ, and 5 phases have been determined as face-centered-cubic, 6 manganese, and hexagonal-close-packed, respectively. At the peritectoid temperature their equilibrium compositions are approximately 5.85, 7.02, and 7.24 wt pct (19.92, 23.2, and 23.8 atomic pct) aluminum."" The transformation might be expected to occur principally at the interface between the a and 5, but such is not the case. Instead, the major part of the transformation occurs by the direct (and perhaps initially diffusionless) conversion of 5 to µ. The composition range of the forming µ nearly overlaps that of the parent at the temperature of transformation" so that little, if any, composition change is required. Transformation proceeds by the nucleation of µ at points upon the external surface of the sample and sweeps through the 5 phase, leaving the a initially almost undisturbed. Subsequently, the a phase participates in the transformation by being partly or totally converted to µ. Specimens approximately 1/4 x 1/4 x 1/16 in. were cut from cast ingots, previously equilibrated 68 hr at 588°C. The specimens were held for 3 hr at

Jan 1, 1958

By Marcel Daly

(A contribution to the study of the conditions of equilibrium of the "free surface" of a water body inclosed in a porous medium.) IN a recent paper, on Geologic Structure in the Cushing Oil and Gas Field, Oklahoma,1 Carl H. Beal has pointed out some interesting peculiarities in the distribution of the hydrocarbons and the disposition of the "planes of separation" between the oil and the water (water surfaces). Mr. Beal's principal statements on this matter may be summarized as follows: I. In every important dome in the Cushing field, which has not been complicated by folding along its sides, the oil area in each, of the three oil and gas sands studied (Layton, Wheeler and Bartlesville) apparently extends farther down on the long axis. of the dome than it does on the steeper sides. The result is that water is encountered at a lesser depth below datum plane (sea level) on the steep sides of the dome than along the ends where the beds are more gently tilted. II. In the Layton and Wheeler sands (to which the detailed study of water surfaces has been almost entirely confined), the water surface is not level, but dips at a gentle angle (maximum dip 100 ft. to the mile) away from the center of the structure. This inclination existed prior to development, and it has been rendered greater by the rapid extraction .of oil and gas. To these statements, the following observations are added. The dominant structural feature in the Cushing field is a broad north and south anticlinal fold, along whose, axis the domes are distributed (Fig. 1, p. 1104), and the more important oil areas in each sand lie on the west side of the field. In many cases, gas has been forced to the east side of the structure, sometimes as far as the water line. From the distribution of the oil and gas bodies, Mr. Beal concludes that the hydrocarbons in this region probably migrated from the west or the northwest.

Jan 1, 1918

By E. T. Turkdogan, P. Grieveson

Molten silver is equilibrated with silicon nitride at 1400°C in nitrogen + hydrogen gas mixtures, and from the solubility data the activity coefficient of silicon is found to be 1.76 at silicon concentrations below 1 pct. Using this value, and that available from the silicon cmbide solubility measurements, together with those derived from the phase equilibrium diagvam, the activities of silver and silicon are estimated for the entire composition range. The main feature of the activity data is that there is a pronounced positive deviation from ideality. The activity of silver in molten silver containing up to 5 pct Si was determined by Schadel, Derge, and Birchenall1 by measuring the vapor pressure of pure silver and of the alloy over a temperature range of 850º to 1050°C. They deduced from their results that there is a positive deviation from Raoult's law and that the activity coefficient of silver increases with decreasing temperature. However, as pointed out by Kubaschewski and Catterall,2 their activity coefficients are much too high, giving silver activities greater than unity. At a later date McCabe and Birchenal13 showed that the previous vapor pressure data on silver4 were high by a factor of about 1.3; presumably a similar error must have occurred with the vapor pressure measurements on the Ag-Si alloys. The activities of silicon and silver calculated by tager' from the phase diagram and by Gibbs-Duhem integration, respectively, show a positive deviation from Raoult's law for silicon activity and positive and negative deviations for the silver activity. According to these computations, at infinite dilution of silicon ygi = 1.12 at 1420°C. d'Entremont and chipman6 measured the solubility of silicon carbide in molten silver at unit carbon activity; the equilibrium silicon content is found to be Nsi = 0.017 ± 0.002 atom fraction for 1420°C. Using the data of Grieveson and Alcock7 for the free energy of formation of silicon carbide from pure silicon and graphite, the activity of silicon for unit activity of carbon and of silicon carbide is asi = 0.0308 at 1420°c; therefore for the above solubility data on silver, YSi = 1.81, which is somewhat higher than that given by Hager. Use is often made of silver alloys in the measurements of activities of solutes in metals where silver has a very low solubility; in fact, Ag-Si and Ag-A1 alloys have been used in the past for such purposes. In an attempt to gain more thermodynamic data on molten Ag-Si alloys, measurements have been made in the present study on the solubility of silicon nitride in molten silver; the results on these solubilities are given in this paper together with a detailed discussion of activities of silver and silicon. SOLUBILITY OF SILICON NITRIDE The standard free energy of formation of silicon nitride is known with a reasonably high degree of accuracy. According to the measurements made by Hincke and Brantle8 and by Pehlke and Elliott,' the following are the free energy data for the standard states of solid Si3N4, liquid silicon, and Nz at 1 atm pressure:

Jan 1, 1963

By J. B. Newkirk, A. H. Geisler

The alloy Cu4Pd has a disordered face-centered-cubic structure when quenched from temperatures between 478ºC and the melting point (about 1100°C). Below 478ºC an ordered phase is stable. The results of a Debye-Scherrer X-ray analysis indicate that the ordered phase has a tetragonal unit cell described by the space group C24h — P42/mt with 2 Cu in 2a, 2 Cu in 2f, 4 Cu in 4j (x = 0.2, y = 0.6), 4Pd in 4j (x = 0.4, y = 0.2), and 8 Cu in 8k (x = 0.1, y = 0.3). The orientation relationship between the face-centered-cubic phase and the ordered tetragonal phase is given by: [100],,. // [130]al,. COO1Ia.d.//COO1I,,.. • The behavior of Cu,Pd is typical of ordering alloys except that the transformation is very sluggish. The increase in hardness and the microstructural and X-ray diffraction effects are interpreted in terms of coherency strains caused by the ordering. AN anomalous construction in the Cu-Pd phase diagram (Fig. 1) was reported in 1939 and has been allowed to stand without further published attention since that time. The odd figuration about the composition 10 to 27 atomic pct Pd is derived mostly from the work of Jones and Sykes.1 Evidently several features of this binary system require further study if the constitutional forms are to be well understood. The present paper includes a study of one of these features, that is, the crystal structure of a single ordered alloy containing nominally 20 atomic pct Pd. This choice of composition was suggested by the work of Harker and associates who determined the structure of Ni4Mo2 and Ni4W.3 The nature of the ordering process in Cu4Pd was studied also by observing the hardness, microstructure, and Debye-Scherrer patterns of specimens which had been aged at various temperatures after quenching from an initial disordering treatment. Experimental Methods A 20 gram ingot of Cu4Pd was made by melting spectrographically standardized copper from Johnson, Matthey, and Co., and commercially pure (99.5 + ) palladium in an argon-filled quartz tube. Chemical analysis showed that the ingot contained 80.0 atomic pct Cu. The ingot was rolled about 60 pct to a strip 0.060 in. thick and was homogenized for 16 hr at 950°C in low pressure argon. Rods cut from the rolled strip were worked into wire 0.015 in. in diameter, and specimens for hardness and microscopic examination were cut from the remaining strip. All specimens, with the exception of some of the wire, were given an initial disordering treatment by heating for 16 hr at 950°C, followed by water quenching. A 10 cm length of as-drawn wire was water quenched after being held in a temperature-gradient furnace4 for 89 days. Room-temperature Debye-Scherrer photograms were then made at points along the wire to determine the temperature below which the ordered phase was stable. Although the accuracy of temperature determination in the gradient was only about ±10 °C, the temperature gradient was sufficiently gradual that the sensitivity was much better and locations which had differed by as little as 1°C could be distinguished. An analysis of the crystal structure of the well ordered alloy was made by X-ray diffraction using a specimen cut from this wire. The change of Debye-Scherrer pattern as ordering progressed was studied by using isothermally aged samples of initially disordered wires. The wires were sealed under low-pressure argon in small quartz tubes for heat treatment. After the aging treatment, the tubes were quenched in water and photograms were made at room temperature in a 10 cm diam camera using filtered Cu kX. (A = 1.540511) Hardness was measured on a Vickers hardness tester using a 10 kg load and 2/3 in. objective lens. Reported values are the average of at least three impressions made on flat specimens 0.060 in. thick. After the hardness of a heat-treated sample had been measured, it was resealed in low-pressure argon and returned to the furnace for continued aging at the same temperature. In this way, two samples served for all aging times at each temperature. Hardness specimens which had been aged 500 hr or more were used for metallographic examination after the final aging treatment. A dilute potassium-dichromate etching solution was used.

Jan 1, 1955

By J. H. Brophy, S. J. Michalik

A constitution diagram for the system Mo-Ir has been determined. The maximum solubility of iridium in molybdenum is 16 at. pct at 2110ºC and decreases to less than 5 at. pct at 1500°C. The solubility of molybdenum in iridium is 22 at. pct. Three intermediate phases appear in the system: 8 MoJr, having the p-tungsten structure; a phase, a cornplex tetragonal structure; and the hcp ? phase. Metallography, melting point determinations, X-ray diffraction and fluorescence, and electron micro-probe unalyses were employed in establishing the diagram. PREVIOUS to the present investigation, the intermediate phases in the Mo-Ir system were identified, but no detailed account of the phase diagram has been reported in the literature. Raub1 investigated alloys of Mo-Ir over an extensive range of composition between the temperatures of 800º and 1600°C. The in-termetallic compound MosIr was found to exist with nearly pure molybdenum, as the solubility of iridium in molybdenum was not detectable parametrically in this temperature range. MO3Ir was found to be iso-morphic with a ß-tungsten type structure, having a parameter of 4.959Å. An intermediate hcp phase, designated as the ? phase, ranged in composition from 52 to 78.5 at. pct at 800ºC, and from 41 to 78.5 at. pct Ir at 1200°C. Parameters noted for the ? phase were as follows: at 42.7 at. pct Ir, a = 2.771i0, c = 4.4366, c/a = 1.601; at 78.5 at. pct Ir, a = 2.736A, c = 4.378A, c/a = 1.600. Molybdenum was found to be soluble in iridium up to 16.5 at. pct Mo (83.5 at. pct Irj, with the parameter of iridium increasing to 3.845A at the solubility limit. Knapton,2 who investigated alloys between 15 and 85 at. pct Ir, essentially agreed with Raub's data, but, in addition, found a a phase in as-melted alloys near 25 at. pcto Ir. The oaphase lattice parameters were a = 9.64Å, c = 4.96Å, c/a = 0.515. The a phase was replaced by the 8 -tungsten phase on annealing at 1600°C. Knapton concluded that the a was stable only at elevated temperatures, and placed the composition of the a phase at approximately 30 at. pct Ir. The intermetallic compound Mo3Ir, with a lattice parameter of 4.965A, was included among the 8-tungsten structures reported by ~eller.' Matthias and Corenzwit,4 and Bucke15 studied the superconducting nature of MosIr, and reported a superconducting transition temperature of 8.$K. The present investigation describes the phase relationships in the Mo-Ir alloy system determined by melting point measurements, X-ray diffraction and fluorescence, and metallography. EXPERIMENTAL PROCEDURES Alloys for the determination of the phase diagram were prepared from powders. Commercial 99.9 pct Mo from Fansteel Metallurgical Corp. and 99.9 pct Ir powder from J. Bishop and Co. Platinum Works were used. The powders were weighed to nominal compositions, mixed, and then pressed, without binder, into compacts weighing 4 to 6 g. These were presintered in uacuo between 1200' and 1400°C for 1 hr, to reduce the degree of spattering during subsequent arc-melting. The compacts were arc-melted in a nonconsumable tungsten electrode furnace six times on alternate sides on a water-cooled copper hearth in an atmosphere of zirconium-getter ed argon at 500 mm of mercury pressure. In almost all cases, this procedure yielded buttons of satisfactory homogeneity. The composition of all melted buttons were confirmed by X-ray fluorescent analysis using the experimentally determined ratio of the iridium La1 line intensity to that of the molybdenum Ka1 line as a function of composition. In this determination four alloys analyzed by wet chemical methods were used as standards. An uncertainty range of ±1 at. pct has been attributed to all indicated compositions. All heat treatments and solidus measurements were carried out in tantalum resistance heating elements in vacuum conditions of 10-4 to 10-5 mm of mercury. A detailed account of this procedure has been reported by Schwarzkopf and Brophy.8 In the heat treatment and solidus measurements of iridium-rich alloys (50 at. pct Ir or greater), a tungsten lining was inserted into the tantalum resistance heating element because of a eutectic reaction which occurs between iridium and tantalum at 1948ºc.7 Heat treatments and solidus measurements carried out at compositions less than 40 at. pct Ir both with and without tungsten linings within the resistance

Jan 1, 1963

By C. Land, R. Hultgren

Heat contents of four Cr-Ni alloys were determined in a diphenyl ethev calorimeter. Aside from ferromagnetic effects, Kopp's law of additivity of heat capacities is approximately fol-lowed, in disagreement with earlier results of A. W. Foster. In 1934 Foster1 reported heat-capacity measurements of dilute solutions of chromium in nickel, primarily as a study of the effect of alloying on the ferromagnetic Curie temperature. He found that, apart from the Curie temperature effect, the general level of heat capacities was reduced 10 pct by the addition of 1 pct Cr; 20 pct by the addition of 2 pct Cr. His measurements of pure nickel essentially agreed with accepted values. These results indicate that small amounts of dissolved chromium cause an increase in the Debye temperature of nickel, presupposing a change of frequency of interatomic bonding vibrations which is much larger than should be expected. If Foster's results were verified, therefore, they would have important implications for bonding theory. The only other heat-capacity measurements in this system seem to be those of Taylor and Hinton,' who studied anomalies which they attributed to super-lattice formation at 25 at. pct Cr. At temperatures above the anomaly, Taylor and Hinton found heat capacities at this composition were quite normal, approximately obeying Kopp's law of additivity. EXPERIMENTAL WORK In order to verify or disprove the remarkable results of Foster, the heat contents of four dilute solid solutions of chromiunn in nickel were measured in a diphenyl ether calorimeter. This instrument, described elsewhere,, operates on the principle of the Bunsen ice calorimeter, but uses diphenyl ether as the working substance. Diphenyl ether melts at the convenient temperature of 26.S°C and supplies a more sensitive measure of heat than ice. The hot sample, in an atmosphere of argon, is dropped from a furnace at a measured temperature into a chamber which is surrounded by a mixture of solid and liquid diphenyl ether. The heat from the hot specimen melts some of the solid without chang- ing the temperature of the calorimeter. The amount of solid melted, and therefore the number of calories released by the specimen, is measured from the increase of volume of the mixture, which pushes mercury down a graduated capillary tube. The apparatus has been standardized against the known heat content of pure platinum. Heat loss during the dropping of the specimen was estimated by comparing the heat content of an empty platinum capsule with a solid platinum ball of the same radius and degree of polish of the surface. Repeated tests demonstrate the precision of measurement to be closer than *0.3 pct. Smoothed experimental results are listed in Table I. The tabulated values for pure nickel are taken from kelley, several measurements were made which agreed closely with this tabulation. For chromium, however, no similar agreement was found. The values tabulated were taken from a thorough study of chromium with the diphenyl ether calorimeter which will be published elsewhere.= Suitable plots of the data showed the expected ferromagnetic anomalies in the low-chromium alloys, while the 11 pct alloy shows no ferromagnetic anomaly, but a different, small anomaly below 900°K. This is perhaps the same anomaly found in CrNi, which was once attributed to superlattice formation,' but is probably due to some other cause, such as antifer-

Jan 1, 1960

By Oliver Bowles

AMONG mining men as well as in the popular mind the conviction has held sway that mining is pre-eminently a western industry. True it is that gold, silver, copper and other metals have made the States of California, Colorado, Montana, Utah. Nevada and Arizona famous. The prominence attained by these States as mineral producers is, however, not measured alone by the money value of the products of their mines. While the metals are without doubt indispensable in industry, the glamour of the precious metals, and the lure of copper, lead and zinc have given to their ore deposits a sentimental interest that often quite out-weighs their commercial importance. Today a great group of more commonplace minerals are finding a place in commerce and industry rivaling that of the metals, but there is little sentiment attached to them, and,. therefore, they attain relatively little publicity. This is the great group of the non-metallic minerals, exclusive of fuels and oils, including stone, sand and gravel, cement, lime, gypsum, asbestos, mica, phos-phate rock and many others. Almost unnoticed they have grown in production to almost unbelievable pro-portions. The estimated value of metal production for 1925 is given as $1,380,000,000, of the non-metals (ex-cluding fuels) $1,294,000,000. The non-metallic industries are not new, many of them date back almost to pre-historic times; but, as the greatest of them (on a tonnage basis) provides raw materials for the construction industries, it required the activities of the present age of construction to bring about their enormous development. Many of them enter manufacturing as well as con-struction. Non-metallic minerals constitute the back-bone of our great chemical industries. While construction and manufacture reach to all parts of the country their widest development has been in the great industrial centers of the eastern Seaboard and the middle West. Consequently the raw materials of mineral origin required for these great industries have attained a remarkable growth in the eastern half of the- United States. In compiling figures of mineral production for 1924, for which more complete data are available than for later years, the surprising fact is brought to light that the non-metallic mineral produc-tion alone of some of the eastern and middle-western States exceeds by a substantial margin the total min-eral production of some of the western States that have been classed as essentially mining States. Thus the non-metallic mineral production, exclusive of coal and petroleum, of the State of Ohio, was approximately $150,000,000; of Pennsylvania $175,000,000; and of New York $107,000,000. For the same year, 1924, the total mineral production of Utah was $84,357,000; of Montana $70,632,000; of Colorado $61,488,000; and of Nevada only $26,226,000. Even Minnesota, with its enormous iron ore production, reached only $107,845,-000, or a sum about equivalent to the non-metallic min-eral production of the State of New York.

Jan 8, 1927

By J. E. Dorn, L. A. Shepard

LOW and Gensamer' demonstrated a number of years ago that the yield point phenomenon in mild steels was associated with the presence of fer-rite soluble carbon or nitrogen. More recently the yield phenomenon in body-centered-cubic metals containing interstitials was rationalized by Cottrell' in terms of a simple dislocation model. Interstitial atoms interact with dislocations in two ways; they cause not only local expansions but induce local tetragonality in the lattice. Consequently, interstitial~ interact with the hydrostatic tension and shear components of the stress about dislocations. They tend to migrate toward the expanded regions of edge dislocations and to assume sites that relieve the shear stresses of screw dislocations. Thus, a dislocation saturated with solute atoms constitutes a lower free energy state than that obtained when the dislocation threads through the average composition regions of the matrix. A greater stress will be required to separate the dislocation from its atmosphere than to move the dislocation through the matrix. This factor gives rise to the upper yield stress, which is required to unleash a series of dislocations in a localized region. This local yielding is propagated across the specimen to form a thin band of plastically deformed material known as a Lueder's band, making an angle of about 45" to the stress axis. Once the band has formed, deformation continues at the lower yield stress by the spreading of the Lueder's band in the direction of the applied stress. Undoubtedly the spreading of Lueder's bands at the lower yield stress is accomplished by the high stress concentrations at the band fronts, which serve to induce continued unlocking of new dislocations in advance of the migrating band fronts. Cottrell and Bilby have shown that the dependence of the yield point on temperature can be deduced by assuming that thermal fluctuations aid the stress in unlocking small dislocation loops from their solute atmospheres. Once a loop that exceeds a critical size has been nucleated, the entire locked diqlocation is released and can migrate. Fisher4 simplified this analysis by assuming that the locking forces were short range, so that if the dislocation loop were displaced only one Burgers vector from its atmosphere, it would be unlocked. Applying his model to the special case of delayed yielding under a constant stress of the order of the upper yield strength, he demonstrated that the delay time 7 for yielding should depend on stress and temperature according to where A and B are constants, G is the shear modulus, and u and T are the resolved shear stress and absolute temperature, respectively. Cottrell and Bilby, Fisher, and Fisher and Rogers' have shown that the above deductions are at least in qualitative harmony with the experimental facts. A number of investigators5-0 have shown that the yield point phenomenon can also be induced in sub-stitutional alloys of face-centered-cubic metals. In general such yield points are not as pronounced as those encountered in body-centered-cubic metals containing interstitials. The yield point phenomenon in these materials is usually enhanced by prestrain-ing at low temperatures and aging at intermediate temperatures. Undoubtedly the yield point phenomenon induced by strain aging substitutional alloys also results from locking of dislocations. But the locking of dislocations in substitutional alloys of face-centered-cubic metals differs somewhat from interstitial locking of dislocations in body-centered-cubic metals. Substitutional elements in face-centered-cubic lattices cause only radial displacements of the adjacent lattice points. Consequently, only the edge components of dislocations can be locked by the mechanism suggested by Cottrell. Additional locking, however, can be obtained by the Suzuki mcchanism.10 In face-centered-cubic metals, dislocations exhibit lower energies when they are present in the

Jan 1, 1957

By D. C. Hilty, W. Crafts

A qualitative pseudoternary solidification diagram for the Fe-S-O system modified by manganese is proposed and supported by experimental derivation of an isothermal section at 1475°C and substantially 1 pct Mn in the solid-metal phase. The solubility of oxygen in liquid iron containing 1 pct Mn and sulphur contents up to 0.9 pct has been measured at 1600°C and found to increase as the sulphur content exceeds 0.15 pct. AS has been pointed out previously,' all oxide and sulphide inclusions in steel, excluding mechanically entrained matter, result from modifications of the basic Fe-S-O system. Therefore, one method of attack on the problem of the mechanism of deoxida-tion and inclusion formation is to examine the influence of deoxidizers on the Fe-S-O liquidus diagram. This approach has been adopted in work on the subject being carried out at the Metals Research Laboratories of the Electro Metallurgical Co. and has resulted in the postulation of types of solidification diagrams for the Fe-S-O system modified with common deoxidizers. This method has been of considerable assistance in interpretation of the factors affecting the formation of inclusions.' For the most part, however, these diagrams have been highly speculative. They were constructed primarily by inference from the pertinent binary and ternary systems and from the appearance of inclusions produced by specific deoxidizers. Moreover, since the systems contain four or more components, simplifying assumptions and qualifications were necessary in order to permit their representation as modifications of the Fe-S-O diagram. Consequently, experimental confirmation of the type of construction employed for these diagrams is desirable, and the present paper is concerned with such evidence. The addition of manganese to the Fe-S-O system was selected for initial investigation. Manganese is an important component of practically all steel and is, therefore, of fundamental interest. Because of its great affinity for sulphur, manganese has a more profound effect on the sulphide side of the Fe-S-O diagram than any of the other common deoxidizing eletments. In addition, more quantitative information pertaining to the contiguous binary and ternary systems involving iron, manganese, sulphur, and oxygen is available than for the other deoxidizers. Fe(Mn)-S-O Solidification Diagram Many of the side diagrams of interest in connection with this system are known. The Fe-Mn binary has been well established by several investigators;% the Fe-O system has been clarified by Darken and Gurry;' and FeO-MnO diagrams have been published by Herty,5 Andrew, Maddocks, and Howat,6 and by Hay, Howat, and White.7 The Mn-O diagram does not appear to have been derived experimentally, but the portion of 'it that is of interest can be visualized easily from a consideration of the melting points of Mn and MnO and the fact that a broad miscibility gap must exist between them. The ternary Fe-Mn-O diagram has been discussed by Benedicks and Löfquist,8 Wentrup,9 and by Körber and Oelsen.10 Experimental study of the Fe-Mn-O system has been carried out by Körber and Oelsen and to a lesser degree by Chipman, Gero, and Winkler,11 Hilty and Crafts," and others. On the basis of published information, then, an outline of the Fe-Mn-O liquidus diagram can be constructed as illustrated by Fig. 1. In this, as in all succeeding diagrams, transformations such as the ?-? reaction in iron have been ignored for purposes of simplification. The arrows denote falling temperature. The distinguishing feature of this diagram is the broad region of liquid immiscibility extending

Jan 1, 1955

By R. Moldenke

The presence of nickel-chromium in pig iron made fro111 Cuban oles is so well known that the word "Mayari" is unconsciously associated with it. Since 1904, when exploration of the Mayari deposits of iron ore in northeastern Cuba was undertaken, there llas been increasing interest in these ores. Tlie Transactions contain numerous references to t1ieln.l This iron ore, which is shipped to the Tinited States in the nodulizecl state, has been thoroughly tested and found very valuable; the deposit covers over 25,000 acres and there is in sight over 500,000,000 tons of ore that, by systematic mining, runs practically constant in composition. With nickel and chromium present, also titanium in sufficient quantities to attract attention, as well as extremely low phosphorus and sulfur contents, the iron founder is naturally interested in the utilization of RInpari ore for pig iron for the better grades of finishrtl iron products. The present point of coilsn~iil)tion ol ILlapri ore is at Sparrow's Poi111, where hlayari pig iron of ally desiretl coml>osition is made. The composition of the dried ore is about as follows: Iron -29 per cent., silica 3 pc.r cent., nickel 1 per cciit., chroiniun~ 1.5 per cent., alumina 11 per cent., ant1 coinbined water 13 per cent. When nodulized, the iron runs up to nearly 56 per cent., the silic:~, :tlumi~i:i, nickel, and c~llromiurn are slightly highr than the arno~l~its just given. Practically all the, combined wntcr is driven off aild the iiodulizccl ore carries only a few- tenths per cent. of 1 C. M. Weld: Residual Rrolvn Iron Ores of Cuba. Tmns, (1909) 40, 299. C. K. Leitll nnd If'. J. Mcncl: Origin of Iron Ores of Central and Northeostr~n rlbn. Trans (1911) 42, 00. C. W. Hayes: May:~ri and Mos Iron-ore Deposits in Cuba. Idem, 109. J. E. Little: Maynri lron Mincs, as Developed by the Spanish-American Iron ('0. Idem, 152. J. F. Iie~np: M'ryari Iron-ore Dcposi(s. Trans. (1915) 61, 3. C. K. Leith 2nd N. J. Mead: Additional Data on Origin of Lateritic Iron 01cs or Eastern Cubn. Tmns. (1916) 63, 75.

Jan 1, 1923

By R. Moldenke

The presence of nickel-chromium in pig iron made fro111 Cuban oles is so well known that the word "Mayari" is unconsciously associated with it. Since 1904, when exploration of the Mayari deposits of iron ore in northeastern Cuba was undertaken, there llas been increasing interest in these ores. Tlie Transactions contain numerous references to t1ieln.l This iron ore, which is shipped to the Tinited States in the nodulizecl state, has been thoroughly tested and found very valuable; the deposit covers over 25,000 acres and there is in sight over 500,000,000 tons of ore that, by systematic mining, runs practically constant in composition. With nickel and chromium present, also titanium in sufficient quantities to attract attention, as well as extremely low phosphorus and sulfur contents, the iron founder is naturally interested in the utilization of RInpari ore for pig iron for the better grades of finishrtl iron products. The present point of coilsn~iil)tion ol ILlapri ore is at Sparrow's Poi111, where hlayari pig iron of ally desiretl coml>osition is made. The composition of the dried ore is about as follows: Iron -29 per cent., silica 3 pc.r cent., nickel 1 per cciit., chroiniun~ 1.5 per cent., alumina 11 per cent., ant1 coinbined water 13 per cent. When nodulized, the iron runs up to nearly 56 per cent., the silic:~, :tlumi~i:i, nickel, and c~llromiurn are slightly highr than the arno~l~its just given. Practically all the, combined wntcr is driven off aild the iiodulizccl ore carries only a few- tenths per cent. of 1 C. M. Weld: Residual Rrolvn Iron Ores of Cuba. Tmns, (1909) 40, 299. C. K. Leitll nnd If'. J. Mcncl: Origin of Iron Ores of Central and Northeostr~n rlbn. Trans (1911) 42, 00. C. W. Hayes: May:~ri and Mos Iron-ore Deposits in Cuba. Idem, 109. J. E. Little: Maynri lron Mincs, as Developed by the Spanish-American Iron ('0. Idem, 152. J. F. Iie~np: M'ryari Iron-ore Dcposi(s. Trans. (1915) 61, 3. C. K. Leith 2nd N. J. Mead: Additional Data on Origin of Lateritic Iron 01cs or Eastern Cubn. Tmns. (1916) 63, 75.

Jan 1, 1923

By J. B. Warriner

S. A. TAYLOR, Pittsburgh, Pa.-What was the distance of haul? J. B. WARRINER.-There is practically no limit to the haul. The length is determined entirely by the feasible location for a dump. -I have known of hauls up to 2 miles in length. R. V. NORRIS, Wilkes-Barre, Pa.-This paper was originally presented to the Anthracite Section as the result of the appointment of Mr. Warriner as the Chairman of the committee to study this matter and present this paper. As he has stated, he obtained data very freely from all the stripping operations in the region, and it is a type of paper of which we should have more in the Transactions. Two or three things in it strike me as particularly valuable. The two tables, 1 and 2, showing the coal remaining, have been the result of a great amount of study, as it is not an easy matter to obtain data as to the amount of coal left in mining. As an example, one of the, anthracite mines was mined and robbed out in 1850, so the maps show. That mine is today producing 250,000 tons of coal, over 50 per cent. from the bed which on the maps is marked as exhausted. What actually happened is that the seam was on a light pitch inconvenient to mine. There was ample thickness of coal and the chambers were driven at a convenient pitch through this 30,-ft. bed, leaving top and bottom, taking out about 10 ft. The pillars were removed and the working caved and marked as gone. That is the type of area that is now being stripped, which explains the reason for the enormous amount of coal left in, and the fact that Mr. Warriner has worked out the actual results from a large number of strippings is of great interest to the operators in any region handling thick coal which has been mined over in the past, generation. The modern mining, of course, is different. We do not have all the coal we want in big veins, and we do not mine it that way. Another interesting feature of the paper to me was the study of losses. It is not uncommon to assume that after you have stripped off the overburden all the coal goes to market. Mr. Warriner has shown that there is a loss ranging up to 10 or 15 per cent. that does not go, so 'that estimates made on stripping, figuring on all the coal, are subject to this very material correction.

Jan 4, 1917

By N. A. D. Parlee, N. M. El Tayeb

Fe-V alloys with small percentages of vanadium show no deviations from Sieverts' Law up to P~, = 1 atm in the 1600º to 1750ºC region. At somewhat under 8 pct V and up to at least 20pct V, at 1604" and 1661 °C, nitrogen absorption follows Sieverts' Law at low Pn2 values, but deviates from this law beyond critical values of pn2, due to formation of a nitrzde phase of approximately VN composition. The behavior below these solubility limits can be described at all temperatures by the equations: RAO and parlee1 suggested that the nitrogen absorption curve for liquid iron alloys takes the general form shown in Fig. 1 when an alloy nitride precipitate is formed. They showed that the precipitation of 6 titanium nitride from liquid Fe-Ti alloys follows this general scheme and dealt with the general theory involved. Recently, Evans and Pehlke2 reported their research on the precipitation of aluminum nitride from liquid Fe-A1 alloys. Fountain and Chipman's recent paper3 on the precipitation of boron nitride from solid solution contains a fine example of the analogous behavior which they have been studying in the solid state. Researches on the absorption of nitrogen by liquid Fe-V alloys have been described by various authors.1,4-7 Most of this work has been confined to fairly low vanadium concentrations and rather high temperatures because of difficulties variously described as, formation of surface scums, bridging, and so forth. This behavior and the rough thermo- dynamic calculations made by chipman,8 over eleven years ago, indicated that excessively high vanadium concentrations should not be required for vanadium nitride precipitation. It seemed desirable to look for and study this precipitation in order to fill out the thermodynamically interesting nitrogen absorption data on these alloys. EXPERIMENTAL METHOD The general method used was essentially the same as employed by Rao and parlee,1 in which a Sieverts type of apparatus was used and the precipitation of the nitride detected by the "break-point" in the Sieverts' Law line, and by the visual observation of the formation of the new phase on the surface of the melt. There were, however, a few differences in apparatus and technique as described below. The oil manometer used by Rao and parlee' to measure low partial pressures of nitrogen was not employed. The present authors sought to avoid as much as possible the exposure of the liquid alloy to low total pressures of gas during the 6 to 10 hr long runs because of the heavy iron evaporation-loss errors involved. This was achieved, partly by keeping evacuation times to a minimum with fast pumping but largely by the use of two burettes, one for argon and one for nitrogen, and using them to equilibrate the alloy with mixtures of argon and nitrogen rather than nitrogen alone. Each run involved a careful sequence of operations. After melting, de-

Jan 1, 1963

By M. A. Orehoski, J. M. Hodge

It is now generally conceded that if a steel is to develop optimum physical properties in the conventionally quenched and tempered condition, the microstruc- ture after quenching should consist wholly of martensite; and that transformation of austenite to intermediate-temperature products during quenching will have a deleterious effect upon the physical properties, particularly the toughness, of the tempered material. This implies that, in order to obtain the optimum physical properties from a given steel, its "harden-ability " should be high enough to suppress all transformation except that to martensite under the heating and quenching conditions to which it will be subjected, and this premise is probably the most important reason for hardenability control. However, the criterion of hardenability that at present is most widely accepted and used is based on a microstructure of 50 per cent martensite. This criterion, which was suggested by Grossmann,' does have considerable justification. It may be readily measured by a fracture or etch test and, since it represents the point at which the hardness is changing most rapidly with variations in cooling rate, it may be determined empirically from a hardness-depth curve by determining the point of steepest slope (the inflection point). Furthermore, in plain carbon steels or in steels of low hardenability, the difference in hardenability expressed in

Jan 1, 1947