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By E. Buehler, H. J. Levinstein

The temperature ranges in which the three inter-metallic phases in the Nb-Sn system form have been determined and the composition and structure of two of the three phases has been established. The kinetics of the formation of Nb3Sn in cored wire samples has been studied in the temperature range of 800° to 1050°C. From 800°to 950°C the rate of formation increases by four orders of magnitude. The rate-controlling step for the formation process in this temperature range appears to be the diffilsion of tin through NbSn. At higher temperatu~es a change occurs in the mechanism of the formation process such that up to a temperature of 1050°C the rate of formation of Nb3Sn does not increase above the rate observed at 950°C. For temperatures helow 950°C the current-carrying capacity of the wire increases with increased percent reaction reaching a maximum value when the formation process is 90 to 95 pct complete. The maximum current-carrying capacity obtainable in this temperature range is independent of the temperature. Above 950°C tlze current-carrying capacity obtainable in the wire decreases with increasing temperature of formation. A model is proposed which accounts for the ohserved behavior. RECENTLY, Buehler et a1.l reported the results of an investigation of the process variables which influence the superconducting properties of Nb3Sn-cored wire. These results indicated that at least four variables affect the properties of the manufactured wire. These include composition, particle size of the starting powder mix, temperature of heat treatment, and time of heat treatment. In order to understand completely the role of these variables, it is necessary to have an accurate knowledge of the phase equilibria in the Nb-Sn system. At the present time, phase-equilibrium diagrams for the Nb-Sn system have been published by a number of investigators.2-5 The diagrams differ as to the number of phases present, the composition of the phases, and the temperature range of stability of the phases. The present investigation was undertaken in order to resolve these differences. Since the investigation of Buehler et al. demon- strated that the length of time at the temperature of heat treatment affected the superconducting properties of Nb3Sn, it is apparent that it is necessary to understand the kinetics of the formation process as well as the equilibrium conditions before a complete understanding of the system is possible. As a result, the kinetics of formation of the various phases in the system were also studied in this investigation. EXPEFUMENTAL PROCEDURE Diffusion couples and sintered powdered compacts were employed in the phase-diagram investigation. The diffusion couples were made by filling 1/8-in.-ID monel-sheathed niobium tubes with tin. The monel sheath was employed to facilitate drawing.' The tubes were then drawn to a tin-core diameter of 32 mils. Samples approximately 3 in. long were then cut from the drawn composite. The tin was drilled out of the ends to a depth of 1/4 in. and niobium-wire plugs were inserted into the ends and peened over. The monel was removed by etching in concentrated nitric acid, after which the samples were sealed in evacuated quartz bulbs and heat-treated in a resistance-wound tube furnace. The samples were quenched into ice water upon removal from the furnace. The diffusion couple samples were examined metallographically employing a chemical etching solution consisting of 10 ml of saturated chromic acid per g of NaF. In addition, two anodizing solutions were used for phase-identification purposes. The first was the picklesimer7 solution; the second consisted of equal parts by volume of 30 pct H2O2 and concentrated NH4OH to which 1 g of NaF was added per 25 ml of solution. The anodizing conditions for the second solution were 2 v and 100 ma with a tin cathode. The powdered compacts were made by pressing previously mixed powders of 99.9 pct pure Sn and 99.6 pct pure Nb supplied by the United Mineral Co. into cylinders 3/8 in. in diameter by 1/2 in. long. The cylinders were then sealed in quartz tubes and heat-treated in the same manner as the diffusion couples. The samples were examined metallographically and by X-ray diffraction techniques. Since it was desirable to be able to correlate the kinetic data with current-carrying capacity, the type of specimen chosen for this part of the investigation had to be a compromise between the optimum system for studying kinetics and one which was suitable for making current-carrying capacity

Jan 1, 1964

By Allen Rogers

TWENTY-FIVE DOLLARS for nothing at all except a sheepskin. That to me is the effect of the New York State law for registration of engineers and the same may be said of any of the state licensing laws. Of course, if one has to practice in more than one state, he must pay a more or less equal amount for every state he works in; and yet there has been little effective protest against these laws. It would seem that the spirit which animated the Boston Tea Party is non-existent amongst engineers. Undoubtedly a good many consider, through their failure to understand the law, that the matter does not affect them. In New York State it is provided that "any person practicing or offering to practice profes-sional engineering or land surveying . . . shall be licensed as hereinafter provided." To quote further from the law: "A person practices professional engi-neering . . . who holds himself out as able to do, or who does, the work that an engineer does . . . " The cunning of the wording of this article can only be appreciated by considering that anyone calling himself an engineer falls within the definition; its liberal inter-pretation (I have not quoted the whole of it) would embrace many who do not consider themselves engi-neers. The state authorities may not construe it to include such individuals; indeed, they may possibly consider it inexpedient to extend it to include engineers of subordinate grade, but the possibility is always there and, even though an engineer be of the grade of assis-tant, he may at any time be called upon to substitute for his principal in responsible charge of the work. It is therefore clear that anyone calling himself engineer and practicing engineering must, for his own protection, apply for registration or run the risk of violating the law. Now, what is the sense of all this? We have done very well without such restrictions on the means of gaining our livelihood. If one only stops to think, there is hardly a minute of his modern existence when he is not dependent for his safety on the engineering by engineers of yesterday or today. How often is one in jeopardy through failure of engineering works, work done under the supervision of those same engineers? If all of us had to wait for our ends by such means, our average life would probably be some thousands of years. Where, then, is the point to the object declared in all these laws that the need for licensing is "to safeguard life, health and property?" Bosh!

Jan 4, 1923

By Paul A. Taylor

MUCH information concerning pegmatites which was thought to be true a few years ago has been proved false, and what is now actually known about some pegmatites is not true of many others. The erratic and seemingly unpredictable structure and variable composition of this class of mineral deposits has been widely emphasized. Even parts of the same pegmatite body exhibit marked differences in texture, mineral composition, width, and attitude. Constructive geological thinking in respect to pegmatites now aims to establish general laws rather than to stress the confusing diversity of features having no special economic significance. Substantial progress has been made in classifying different types of these deposits according to general features, internal structure, mineralogy, and origin. In some cases it has even been possible to block out tonnage reserves in advance of mining. It is still easy, however, to make highly erroneous predictions after a preliminary examination of a pegmatite prospect. Pegmatites are important to the economic well being of the country and to its military security. They furnish virtually all the feldspar, strategic mica, beryl, columbium, tantalum, and caesium utilized in the United States, as well as sundry other minerals and significant amounts of lithium and rare earth minerals and gems. With the exception of vermiculite, occasional ilmenite-rutile, and perhaps soda-lime feldspar and garnet deposits, basic pegmatites are of little economic importance. Consequently in this paper, as in common parlance, the term pegmatite generally relates to coarsegrained acidic rocks or what is aptly called giant granite. Available data indicating the size and importance of the production and trade in specified pegmatite minerals are summarized in Table I. Geological Features Much of the latest thinking on the economic geology of pegmatites is now available in a 115-page monograph' by a group of experts who participated with geologists of the Federal Geological Survey in the widespread wartime investigations. Doubtless the most significant feature of the monograph is indicated by the title, The Internal Structure of Pegmatites, but it also contains a vast amount of other new information and includes the assimilated concepts of many earlier writers, whose works are given in a comprehensive list of references. The shape, size, attitude, and continuity of many pegmatite bodies is controlled by the structure of the older rocks in which they occur. If the older rocks are easily penetrated, e.g., biotite schist, most of the pegmatites in a given district will be found outside the parent granite mass as exterior pegmatites. Marginal pegmatites are more prevalent if the older rocks are massive, unsheared, and sparingly jointed. Networks of pegmatites are abundant in highly-jointed rocks. In strongly foliated schists the bodies are usually lenticular, whereas in highly-folded areas they assume tear drop, pipe or pod-like, bow-shaped, or sinuous forms. Jahns2 recognizes five major shape classes: l—dikes, sills, pipes, and elongate pods; 2— dikes, sills, pipes, and pods with bends, protuberances, or other irregularities; 3-—trough-or scoop-shaped bodies with or without complicating branches; 4—bodies with the form of an inverted trough or scoop; and 5—other bodies, including combinations of the above and miscellaneous shapes. Many pegmatite deposits are scarcely big enough to be recognizable as such. Most of them, in fact, are small tabular deposits less than 4 in. wide and usually without economic concentrations of minerals. On the other hand, some pegmatites are more than a mile long and over 500 ft wide. The ratios of length to breadth range from 1 : 1 to 1 : 100. Although the vertical dimension bears no invariable relationship to strike length, tabular deposits or large lenses are often symmetrical enough to show nearly as much continuity down dip as in their horizontal extension, and some pipes or pods are amazingly persistent in the vertical plane. Small pegmatites often string along a fairly definite trend line; in a given district major bodies may lie roughly parallel, and where only a few of them do not, the erratically disposed bodies generally differ in composition from those conforming to the regular pattern. This does not apply, however, in all districts. Characteristically, pegmatite veins pinch and swell or split into branches. When they pinch out entirely it is often possible to find a new body by prospecting the extension of the strike or dip, but the chances of finding a hidden deposit are ordinarily too uncertain to justify much subsurface prospecting. Diamond drilling may yield valuable information as to the continuity of known deposits whose upper portions are well-exposed. Some deposits, in fact, can be proved up for hundreds of feet by surface trenching and then intersected by drill holes at various depths like any other vein-like deposit. Others twist and branch, apparently defying all efforts to explore them short of actual mining.

Jan 1, 1954

By William Hurst

Muskat's depletion performance equation is here derived considering the expansion behavior of the reservoir hydrocarbon system and a simple fractional-flow equation. This nietkod of derivation leads logically to the two extensions that follow. The first of these is concerned with gravity segregation in a depletion-drive reservoir. The second is concerned with including an empirically determined tern? for water influx in the performance equation. The more general equation for gravity segregation when there is a primary gas cap and empirically-determined water influx is stated for completeness. These equations have been found useful in reservoir performance calculations in Eastern Venezuela. A discussion on the methods of solving these equations follows, and considers firstly the effect of taking finite intervals in the numerical integration, and sec-ondly, methods of incorporating the time functions involved in segregation in with the expansion behavior. The paper concludes with a brief general discussion on further extensions to the depletion performance equation. INTRODUCTION The two fundamental sources of energy by which oil is produced from a reservoir result from pressure depletion inside the boundaries of the reservoir and fluid encroachment across the boundaries of the reservoir. The wells in either case form low pressure outlets through which oil and gas may be produced by the expansive force of the reservoir fluids and associated encroaching fluids. When the reservoir pressure is higher than the bubble-point pressure of the oil, so that there is no free gas in the reservoir, these expansive forces are the only ones available for the production of oil. However, when the reservoir pressure is less than the bubble-point pressure of the oil, free gas is vaporized as the pressure falls. With both oil and free-gas phases present, the additional forces of gravity and capillarity may operate on the gas-oil system, as they have previously operated on the oil-interstitial water system. Gravity tends to segregate the free gas from the oil due to their density difference. Capillarity opposes and eventually balances gravity as the more extreme free gas and oil saturations are reached, preventing the independent move- ment of free gas until it is above a certain saturation, and the independent movement of oil when it is below a certain saturation. The type of depletion performance equation chosen for predicting the future performance of a reservoir depends on the amount of past history available. When the reservoir is somewhere past the halfway mark in depletion, some form of decline curve is often used. With less past history, material balance equations which incorporate empirical factors based on the past performance are often used. When, however, the amount of past history is small, the Muskat depletion performance equation will usually be used. The distinguishing feature of this type of equation is that empirical factors based on the over-all or macroscopic reservoir behavior are almost or entirely absent. Each parameter affecting the reservoir performance is ascribed an independent set of values based on measurements made on laboratory samples; that is, incorporating microscopic empirical factors. In establishing Muskat-type depletion performance equations, it is necessary to consider the reservoir as consisting of a number of associated blocks, in each of which the saturations and pressures may be considered uniform, and in each of which all substances have uniform pressure-volume characteristics. Thus, a primary gas cap can usually be considered as one block and an aquifer as another. Gravity segregation may be negligible for practical purposes when the rock and oil properties are adverse and/or the dip or thickness of the reservoir is too small. In this case the whole oil leg may be considered as one block, except in very large reservoirs. In very large reservoirs the fluid and rock properties may vary enough, particularly in the dip direction, for it to be necessary to divide the oil leg into a number of blocks, in each of which the relevant quantities may be considered uniform. When gravity segregation of the oil and free gas is not negligible, it is necessary to consider the space occupied by the initial oil leg as divided into two blocks, a secondary gas cap and an effective oil leg, in each of which saturations may be considered to be uniform. The total volume of these two blocks is thus constant, but the secondary gas cap grows continuously at the expense of the oil leg. Muskat1 derived depletion performance equations for the basic case of an oil reservoir with closed boundaries and without segregation, and for the case of an oil

R. C. Canby, Wallingford, Conn. (communication to the Secretary*). —Apropos of the experimental reduction of copper from cuprous chloride by fusion with ground limestone and colre, as described by Messrs. Laist and Frick, and also proposed for use at Chuquicamata, it might be of interest to refer bricfly to the experience at Argentine, Kan., in the smelting of the suboxide of copper (as produced in the Hunt and Douglas process) containing appreciable quantities of chlorides. In the Engineering and Mining Journal of June 10, 1911,I gave some account of what had appeared to be crucial difficulties with the Hunt and Douglas process, and how the filter-press difficulty had been so rapidly overcorne after my discovery of the effect of the sodium salts in the leaching solutions. I also described the effect of the cupola-furnace gases upon the lime rock with which I had replaced the coke in the absorption tower, which apparently showed the presence of considerable chlorine, due to the imperfect conversion of the subchloride to suboxide, as well as that due to the difficulties of washing thoroughly the suboxide with the means provided, and also to the presence of chlorides in the cement copper which was smelted with the suboxide. The fumes from the cupola, when issuing direct into the atmosphere, were very dense and white, except when a hot furnace top caused a reddish tinge due to dust. These fumes had a peculiarly suffocating effect, SO that when they were blown over into the town the population suffered the greatest actual distress, not the mere annoyance which would have been due to a disagreeable odor. The absorption tower had been built at the instance of the city authorities to abate this nuisance, and not with the idea of making any additional metal savings. A serious feature in connection with the Argentine experience with the Hunt and Douglas process was, that it had been implicitly assumed that there could be no metal loss in the Hunt and Douglas process itself, and that all attempts to locate the ruinous copper losses which were accumulating in the metallurgical accounts were devoted to the roasting department. It is possibly unfortunate for metallurgical advance along these particular lines that just about the time of this discovery of this previously unsuspected volatilization loss, in the smelting of the suboxide, the Kansas City company made a contract with the Western Union Telegraph Co. for its supply of copper sulphate and the Hunt and Douglas

Jan 1, 1915

By Ursula E. Wolff

The precipitation of carbides from an alloy containing 33 pct Ni, 21 pct Cr, balance iron, was investigated electron microscopically by means of extraction replicas and thinned metal foils. Annealing temperatures ranged from 565°to 870°C and up to several thousand hours. M23C6 precipitated in pain boundaries, incoherent and coherent twin boundaries in that sequence. The orientation relationship between carbides and austenite matrix was determined and correlated with the morphology of the carbides and with the type of boundary in which precipitation occurred. In large-angle grain boundaries, as well as in coherent twin boundaries, the carbides had the same orientation as one of the adjacent pains. These carbides formed sheets of individual flakes with shapes related to the orientation of the boundary. In incoherent twin boundaries carbides precipitated in ribbons composed of pavallel rods. An unidentified subcarbide was found to precede precipitation of M23C6 in these boundaries. The M 23 C6 rods had a kind of fiber texture with (110) parallel to the long dimension of the rods and ribbon, and with orientations of both of the adjacent twin-related austenite crystals Predominant in the texture of the carbide. A hard sphere crystal model has been used to discuss orientation and morphology of the carbides in terms of free volume and vacancies available in the boundaries. A number of papers have dealt with the morphology of chromium carbide (M23 C6) precipitated in austenitic stainless steels.1"7 In all these investigations, the carbides were examined in the electron microscope by means of extraction replicas. With this technique, the carbides retain the spatial distribution they had in the bulk sample. However, since the matrix is dissolved in the process, the particles can turn in an unpredictable way; and the orientation relationship between matrix and carbides cannot be established. In this paper the results of studies on extraction replicas and on thinned metal foils are reported. These studies were undertaken to determine the matrix-to-car bide orientation relationship, and to correlate the orientation of the carbides with their morphology. PROCEDURE The material used was an austenitic alloy with 33 pct Ni, 21 pct Cr, balance iron, containing approximately 0.05 pct C. Coupons of 1.25-mm sheet were first solution-annealed at 1050°C for 15 min and air-cooled. Then, to precipitate the carbides, samples were isothermally annealed in the range from 565" to 870°C for times up to several thousand hours. All further specimen-preparation procedures were carried out after the final anneal. Carbon extraction replicas from polished and etched surfaces were made with 10 pct bromine in methyl alcohol.' Thin foils were prepared from punched-out 3-mm-diam disksg which fit into the electron-microscope holder. The disks were prethinned by grinding to approximately 0.5 mm thickness, and then electro-polished in a polytetrafluoroethylene holder1' with a solution containing 5 pct perchloric acid in acetic acid to which 10 g per 1 Cro3 and 5 g per 1 nickel chloride were added (etchant modified from that of Briers et al."). This solution dissolves neither the carbides nor the austenite around the carbides preferentially. By using extraction replicas, electron micrographs and selected-area electron-diffraction patterns were taken from the same carbide arrays. By using thin foils, electron micrographs were made from a grain boundary area containing carbides. Electron-diffraction patterns were then taken from the same area and from each of the adjacent grains separately. In this manner, the orientation of each grain could be determined without interference by the carbide pattern. A peculiarity of extraction replicas should be pointed out. After the matrix is etched away, the carbide arrays float freely in the etching and washing solutions, and are held in place only at the anchoring points in the carbon replica. When the replica is picked up with a screen the carbide arrays tend to flip to one side. Thus, while the surface features are preserved, the original arrangement of the carbides may severely and unpredictably be disturbed whenever the specimen contains large amounts of interconnected carbides. Nevertheless, it is possible to correlate the different morphologies of the carbides with the type of boundary in which they have precipitated. RESULTS 1) Extraction Replicas. Fig. 1 shows that the grain boundaries usually are curved, multicornered surfaces of random orientation. The coherent twin boundaries (which are (111) planes) cut a grain into parallel slices. Incoherent twin boundaries occur at the ends and on the steps of twins and are often narrow, parallel-sided strips which are much longer than they are wide. Different morphologies can clearly be distinguished for the M23Ce carbides precipitated in each of these types of boundaries, and agree well with those observed by kinzel.2 The kinetics of this precipitation has been investigated." The first carbides precipitate in junctions of three grain boundaries and fan out from there into the adjoining boundary surfaces, Fig. 2(a). These carbides are oriented randomly, Fig. 2(b), and become coarser and thicker as annealing time increases. The large-angle grain boundaries are next to fill

Jan 1, 1967

AIMS 1953 DIRECTORY SUPPLEMENT OFFICERS AND DIRECTORS 1953 President and Director ANDREW FLETCHER (2) New York City Past President and Director MICHAEL L. HAIDER (2) New York City President-elect and Director LEO F. REINARTZ (3) Middletown, Ohio Vice-Presidents and Directors 0. B. J. Fraser (2), New York City J. L. Gillson (1), Wilmington, Del. A. B. Kinzel (3), New York J. B. Morrow, (2) Pittsburgh, Pa. L. E. Elkins (3), Tulsa, Okla. * T. B. Counselman, Stamford, Conn.

Jan 1, 1953

By Terkel Rosenqvist

J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—The fact that the experimental work has been applied to copper rather than iron and that the paper is presented to the Iron and Steel Division, I regard as rather significant. It shows the unity of metallurgy and the fallacy of trying to cut it up by metals. This result for the solubility of sulphur in molten copper correlates with Professor Schuhmann's finding that the published data on the other side of the copper-sulphur miscibility gap are also in error. I should like to ask the author to say a little bit more about the sulphur capacity of the slag. T. Rosenqvist (author's reply)-—I hope that Dr. Chipman will find the derivation of the expression for sulphur capacity more clearly explained in the printed version of the paper than in the oral discussion at the meeting. I feel that this quantity, which actually is the ratio of two activities, can be measured more easily than the individual activities. Even if the ratio CaO/CaS is chosen as the standard state, the expression can be used for any slag, even for slags completely free of lime, and it represents a way to put the desulphurizing power of all slag constituents into one bag. Some doubt has been expressed as to whether oxygen ions really exist in calcium oxide and in molten slags. From a thermodynamic view point that question is of minor importance. The term oxygen ion activity, or any activity for that matter, is defined rigorously by the equation: activity = exp p/RT, where p is the change in free energy connected with the transfer of one mol of ions from the standard state into the slag. Whatever happens to the ion in the slag is of no concern to the thermodynamicist. Regardless of whether the ion is "free" in the slag or not, or whether it is present in a very small amount, its activity can always be expressed, and for a thermo- dynamic calculation that is all we need. However, ionic activities will only be of some real value if they are simple functions of the slag composition, or can be measured easily. Concerning the real nature of the oxygen in the slag, my feeling is that the oxygen atom has a rather multiplex nature depending on how strongly it is tied by covalent forces or polarized by the other atoms or ions present. The oxides of iron, cobalt, and nickel differ from calcium oxide and blast furnace slags as to the amount of free electrons that can give rise to electronic conductivity. In slags we know that the conductivity is mostly ionic. The fact that reversible emf's can be obtained with oxygen electrodes in certain salt melts, indicates a significant amount of oxygen ions in these melts. But extended work, e.g. polaragraphic studies and measurements of transference number; are needed to obtain quantitative information about the real structure of the slags. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—-With reference to the ion, it might be well to remember Dr. Moses Gomberg. All of his life he had no use for the ionization theory and he contributed greatly to the field of chemistry on the assumption there was no such thing as ions. I do not think we have to worry about whether the oxygen is ionic or not. I think one thing specifically should be brought to your attention and this I think is one of the important contributions of Dr. Rosenqvist. He pointed out what we know as oxygen potentials or what is described as oxygen potentials. I have used this concept for a long period of time and I want to state that if this concept is properly applied, it vitiates much of what we have in the literature, or makes our usual ideas regarding oxidation seem primitive. That one thing is more valuable than almost all the rest of the discussion as a fundamental basis on which to build a reasonable in-

Jan 1, 1952

By G. Ferrara

The reserves of lead and zinc ores in the metalliferous district of Iglesias in south-western Sardinia are today estimated at about 30 million tons, grading from 4 to 10% Pb + Zn. Of these reserves, about 40% are in the mines owned by AMMI Sarda S.p.A. The working of these resources goes back to ancient times. Not infrequently, traces of old Roman workings and remains of ancient implements are come upon in the higher parts of some of the ore bodies. Exploitation of these mines on larger scale, however, dates from the middle of the 18th century. Initially, the more accessible zones of the ore bodies and the richer ores were worked - the galena and the rich oxidized ores (calamine* with 25-35% Zn), which were often found in large masses, the enormous empty cavities of which still remain. The poorer grade deposits have been gradually rendered workable by the development of technology - the perfecting of the

Jan 1, 1970

New York Holds monthly meetings, except June, July and August J E SPURR, Chairman A D BROKAW, Vice-chairman SIDNEY ROLLE, Vice-chairman M H MERRISS, Secretary-treasures, Nichols Copper Co, 25 Broad St, New York M F CHASE KARL HOFFMAN Boston Meets first Monday of each winter month C R HAYWARD, Chairman E C GEITHER, Vice-chairman D H McLAUGHLIN, Secretary-treasurer, Rotch Bldg, Harvard Univ Cambridge, Mass GEO H GILMAN GEO A PACKARD

Jan 1, 1923

By Elmars Ence, Harold Margolin

The titanium-aluminum system has been investigated in the composition region 0 to 34 pct Al in the temperature range 800" to 1450°C. The phases encountered in this region were: a,ß, TiAl3, The reactions observed are as follows: 13 ; L - 6T. A1, 0 (15 pct Al) + 6 (18 pct Al) - yTi Al (16.5 pct Al) at -1170°C andP (7 pctpct Al) + y (9.2 pet Al) - ah(9 pct Al) at - 1060°C. A eutectoid reaction: y — a +d belm 700°C is postulated. THE Ti-A1 system has been the sub.ect of a number of investigations. Several of these1-3 have indicated extensive solubility of A1 in both a and ß titanium. Ence and Margolin, as a result of work on the Ti-A1-0 system:'5 have shown that the a solubility ofalumi-num is considerably restricted, and found that a compound, Ti2A1 existed in the region formerly designated as Q a This structure was identified as hexagonal with c/a = 0.803. Pietrokowsky confirmed the existence of this phase7 and pointed out that the structure was isomorphous with Ti3Sn.8 Although the existence of Ti,A1 has been confirmed by others,9-12 there has been considerable disagreement regarding the composition and mode of formation. A detailed reinvestigation of the Ti-A1 system has been published by Sagel et al.13 The tentative diagram indicated two phases, a, and e, occurring in the former all a region. The a, phase has the same structure as Ti2A1 and was indicated as having a broad region of solubility. Epsilon, a tetragonal phase, was shown to form within the a, solubility region. AS a result of unpublished work,14 Ence and Mugy3 olin disagreed with the interpretation of Sage1 et al., although some common features existed. The present study was conducted in an attempt to clarify prevailing uncertainties. EXPERIMENTAL PROCEDURE Alloy Preparation—Alloys were prepared from iodide titanium (99.9 pct Ti with less than 0.01 pct Zr) or Bureau of Mines electrolytic titanium (BHN-73) and high purity aluminum (99.99 pct). Alloys were arc-melted in argon or helium atmosphere as 15-g buttons in the composition range up to 34 pct Al. Depending on need, alloys were made in increments varying from 0.25 to 2 pct Al. Up to five 15-g buttons of some compositions were made. Weight losses during melting did not exceed about 1 pct of the charge and chemical analysis revealed that both titanium and aluminum were evaporated. In general, nominal and analyzed compositions agreed within 0.5 pct and therefore nominal compositions were used in plotting the data. Unavoidably, some overlap of composition occurred, particularly where small increments of A1 were used. The small increments were primarily used to obtain alloys which would fall into the narrow a -, r region and this purpose was achieved. In general, the data obtained from Bureau of Mines base titanium and iodide titanium alloys were in agreement. Forging—Both as-cast and forged samples were employed. Samples were heated for hand forging by an oxygen-hydrogen torch to the region 1200" to 1300°C. A titanium anvil and cover plate were used to prevent any iron pick-up and consequent formation of a low melting point compound. Frequent reheating kept the temperature in the desired range. Under these conditions, alloys containing up to 15.5 pct could be successfully forged. To check on the depth of contamination, forged alloys were heated slightlybelow the ß transformation temperature. Metal was removed to a depth below the contaminated surface so revealed, and the subsequent results obtained from these samples agreed closely with those secured from as-cast material. Heat Treatment—Prior to heat treatment, all alloys were vacuum annealed to remove hydrogen. Samples

Jan 1, 1962

President-Mrs Andrew E Beer, Richardson Ave, Sea Cliff, L I, N Y First Vice-President-Mrs Lyman H Hart, 6-F Essex House, Garth Woods Apts, Scarsdale, N Y Second Vice-President-Mrs John R C Mann, 90 Edgemont Road, Scarsdale, N Y Third Vice-President-Mrs Edward P Chapman, Jr, 2632 Vista Larga Dr N E, Albuquerque, N M Fourth Vice-President-Mrs R A Cattell, 7717 14th St, N W Washington 12, D C

Jan 1, 1959

FREDERICK G. BRENNEMAN Frederick G. Brenneman died of pneumonia at his home at Pottsville, Pa., on November 24. He was in the class of 1912, of the Pottsville High School, attended Bellefonte Academy, and graduated from the Colorado School of Mines, at Golden, Colo., in 1916. He is survived by his parents, Mr. and Mrs; Philip Brenneman and three brothers, Louis P. and Robert C. at home, and John :F., of Camp Merritt, N. J. Mr.

Jan 1, 1919

By W. N. Lacey, R. H. Dourson, B. H. Sage

THE compositions of coexisting phases in the methane-propane-n-pentane system were determined at 160° and 220°F. throughout the two-phase region, at pressures above 500 lb. per sq. in. The experimental results permitted the calculation of gas-liquid equilibrium constants as well as the establishment of the critical behavior of this ternary system. The experimental results are presented in tabular form and a number of diagrams illustrating the phase behavior of this system have been included.

Jan 1, 1942

[ZAY JEFFRRIES, Vice-chairman PAUL D, MERICA, Chairman W, M, CORSE, Secretary Executive Committee J. It, FREEMAN, JR., Local Section S. SKOWRONSKI, Papers Committee R. S, ARCHER, Non-ferrous Data Sheets H, C, JENNISON, Membership Committee E, C, BAIN, Journal Committee L, W. SPRING Local Section Committee J. R, FREEMAN, JR,, Chairman R. J, ANDERSON, Cincinnati R. L. DOWDELL, Minneapolis R. S. WILLIAMS, Boston G, H, CLAMER, Philadelphia W. A. SCHEUCH, Chicago R, F, WOOD, New York]

Jan 1, 1928

By John M. Tinsley, Calvin D. Saunders, H. K. van Poollen

In the past few years much con-sideration has been given to the evaluation of the effect of hydraulic fracturing on the productivity of wells. Generally, these studies included the evaluation of fracturing materials, fracture extension and formation damage due to the use of various fracturing fluids. Only little consideration has been given to the characteristics, and in particular the flow capacity, of the fracture itself and its effect on well productivity. This paper presents the results of laboratory investigations pointed toward fie evaluation of the efficiency of various fracrures with special emphasis on the flow capacity of these fractures. Data presented in this paper are the results of both an electrical model study and physical testing. Under consideration are (I) effect of overflush, (2) premature production of well after treatment, (3) "tailing-in" with coarse sand near the end of the treatment, (4) effect of propping agent size and concentration, (5) reduction in effective frac-ture permeability caused by formation caused by formation fines, silt and clays, and (6) effect of various fluids on formation strength and competency. The results of this investigation indicate that the flow capacity of a fracture is affected by any or all of the various parameters mentioned above. The authors believe that a better understanding arid utilization of these factors should result in more efficient formation fracturing. INTRODUCTION Hydraulic fracturing has become almost a standard practice of many companies for stimulating production from old and new wells. Although most companies utilize this service, techniques of application vary widely between companies and areas. Probably too often when a well in an area responds favorably to a particular technique all future wells in the same area are treated in a similar manner. Possibly a modification of the technique would result in a further production increase. Variables, of which many are extremely difficult to evaluate from field results, hamper the selection of procedure changes. Attempts are being made by a number of organizations to analyze statistically treating techniques from production data. This is a very worthy and necessary approach but very possibly laboratory investigations may aid in evaluating some of the variables which tend to affect the results of a fracturing treatment. Some of the factors cannot be studied from practical field experience and only laboratory tests can show the possibilities which might exist. One of the factors which appears to be of major concern today is the flow capacity of the created fracture and how it can be changed. Papers on this general subject have been primarily concerned with the size of propping agent and the extent of fracture. Papers have also been written on the possible permeability damage to formations by fracturing fluids. In addition, it might be possible that another type of flow restriction is prevalent. This would be a restriction of flow through a sand-packed frac- ture caused by foreign materials integrating within the propping agent. This paper presents preliminary data obtained in an attempt to evaluate the effect of some factors affecting flow through sand-packed fractures. No attempt is being made to offer a fracturing technique adaptable to all areas and conditions, but to furnish data tending to show the possible effects which might be caused by variations in procedures and materials. PROPPING AGENT PERMEABLLITIES A hydraulically induced fracture containing sand as a propping agent may theoretically be classified as a packed-sand system. The flow of fluids through such packed systems has been the subject of much research. Although there have been numerous methods proposed for the evaluation of such systems, most writers agree on the general properties affecting their flow capacity or permeability. These properties include porosity, particle size, sphericity and the roughness of the particle. In some methods of evaluation . the particle size and sphericity terms are combined to produce an equation which is a function of the surface area of the particles. In this study the permeability of various fracturing sands was both measured and calculated. The apparatus for the permeability measurements consisted of a 52-in. Lucite tube with a 2.5-in. ID. A screen and drain plug were fitted in the bottom of this tube to retain and hold the sand in place while allowing fluid flow. Two pressure taps consisting of thin, highly perforated

By Edward N. Trump

EXTENSIVE beds of rock salt occur in New York, Michigan, Kansas, and Texas. Wells are drilled through the beds, cased, and equipped with a suspended center tube. By circulating water through such a well, the soluble saline is dissolved and a brine produced. Operation of a well results ordinarily in the formation of an inverted conical cavity in the saline, inasmuch as the dissolving action of the fresh water is more rapid at the top of the bed than at the bottom. Under continued operations, the side wall of the cavity becomes so flat that a blanket of mud is deposited thereon and if the bed is overlain with shale or a soft rock caving follows. Three methods of operating wells have been employed-the "Tully plan," "the Detroit plan," and "the Trump plan." Both the Tully plan and the Detroit plan involve the formation of the aforesaid conical cavity with constant caving of shale above and deposition of mud on the side wall; the Trump plan was developed to avoid both these circumstances and thus materially prolong the life of a well. Details of the three plans follow. THE TULLY PLAN In the Tully plan, the water passes down the annular space between the casing and the center -tube, the brine rising in the center tube (Figs. I and 2). An inverted conical cavity is formed, the side wall of which relatively soon becomes so flat that it is blanketed by mud and impurities from the rock salt; this blanket limits dissolving action to the perimeter of the base of the cone, situated at the top of the saline bed. Caving of the overlying strata follows, and the total production of brine from the well is comparatively small. THE DETROIT PLAN In the Detroit plan, the water passes down the center tube, the brine rising in the annular space between the center tube and casing (Figs. I and 2). Initially, this flow forms a pear-shaped cavity in the bottom of the salt bed, but this cavity soon changes in shape to that of an inverted cone, as under the Tully plan, with the attendant disadvantages inherent in that plan. Application of the Detroit plan is limited to salt beds 300 ft. thick as a minimum. This depth of bed is necessary to prevent fresh water of lower specific gravity than the brine from rising in the

Jan 1, 1944

E. H. Dix, JR., Chairman L. W. M. PEIRCE, Past-chairman R. F. MEHL, Vice-chairman ALBERT J. PHILLIPS, Vice-chairman E. M. WISE, Secretary International Nickel Co., Bayonne, N. J. W. M. CORSE, Treasurer LOUIS JORDAN, Executive Secretary 29 West 39th St., New York, N. Y. Executive Committee W. H. BASSETT, JR. R. H. LEACH' W. H. FINKELDEY W. E. REMMERS2 J. A. GANN H. J. ROAST G. O. HIERS C. S. SMITHS L ZICKRICK

Jan 1, 1936

By Strathmore R. B. Cooke, Eugene L. Talbot

THE perfluoro acids and derivatives show unusual surface-active properties that qualify them as possible flotation reagents. They lower the surface tension of water from 15 to 20 dynes below that obtainable with the corresponding hydrocarbon compounds.1, 2 Fluorochemicals adsorb very strongly on solid surfaces to give films that exhibit larger contact angles than films of the corresponding hydrocarbons."' * The large contact angles probably result from the terminal —CF3 group. The perfluoro acids are made by electrolysis of the corresponding carboxylic acid in anhydrous hydrogen fluoride.5 From the perfluoro acids many derivatives may be obtained, such as amides, amines, alcohols, xanthates, ethers and esters and others. Since the fluorinated analogues of the conventional hydrocarbon flotation collectors possess enhanced surface properties, a few were selected for testing. Because a survey of all possible minerals and reagent combinations would be out of the question, hematite was chosen to represent a nonsulphide system and pyrite to represent a sulphide system. The fluorinated reagents used in these experiments were prepared in the research laboratories of Minnesota Mining & Mfg. Co. Some were synthesized especially for this research. They are not available cokmercially. Separation of Nonsulphide Ores: The separation of oxides from silica has always been a challenge to the flotation industry because differences in surface properties of the minerals are normally insufficient to produce clean concentrates. Oleic acid," rosin acids,' and amine salts% ave been used to considerable extent to effect separation of metal oxides and silica. The system hematite-silica was chosen to represent the nonsulphides both because of its difficulty of separation and because large tonnages of easily obtainable material are available, such as gravity concentration tailings and nonmagnetic taconites on the Mesabi Range. The wash-ore tailings used here contained approximately 35 pct iron after desliming. Samples of the material used in this work were part of the same lot used by Chang, Cooke, and Huch9 and were prepared in an identical manner. Reagents for Nonsulphide Ores: Since one of the purposes of this investigation was to compare hydrocarbons with fluorocarbons, reagents of known behavior such as oleic acid, and the alkali metal salts of certain resin acids (Dresinates), were established as standards. Hydrocarbons and fluorocarbons of comparable chain length and other experimental fluorocarbons were tried as collectors for hematite. A list of the materials used and the concentrations of their stock solutions are given in Table I. Since silica can be selectively floated from hematite by conventional reagents," a few fluorocarbon reagents were also tried for this purpose. Their composition and concentrations are given in Table 11. Most of these reagents served the dual function of collector and frother. In the case of F-11 flotation did not occur but it served as a frother when F-6 was employed as a collector. Reagent grade sulphuric acid and sodium hydroxide were used to regulate the pH. Deionized water containing less than 0.1 ppm of salts expressed as NaCl was used for all solutions and flotation tests. The pneumatic flotation cell consisted of a 350-ml fritted glass Buechner funnel with a source of filtered air which could be controlled by a needle valve." A 50-g sample of ore and 250 ml of deionized water were added to the flotation cell and stirred slowly. The reagents were added and the pulp was conditioned before air was admitted to the cell. Approximately 15 ml of the pulp were removed for pH determination before flotation was started and were then returned to the system. The pH was again measured after flotation. Air was admitted to the cell until no further flotation occurred or until the character of the float changed markedly. Both the float and the nonfloat products were filtered, dried, weighed. and assayed for iron. The cell was washed in hot water and rinsed with deionized water after each test. Occasionally the cell was cleaned with concentrated hydrochloric acid to remove iron oxide particles from the glass frit. Experimental Results: Above a pH of 8, sodium oleate was an effective collector for hematite. The emulsification of equal parts of heavy fuel oil (20"

Jan 1, 1956

By Edward N. Trump

Extensive beds of rock salt occur in New York, Michigan, Kansas, and Texas. Wells are drilled through the beds, cased, and equipped with a suspended center tube. By circulating water through such a well, the soluble saline is dissolved and a brine produced. Operation of a well results ordinarily in the formation of an inverted conical cavity in the saline, inasmuch as the dissolving action of the fresh water is more rapid at the top of the bed than at the bottom. Under continued operations, the side wall of the cavity becomes so flat that a blanket of mud is deposited thereon and if the bed is overlain with shale or a soft rock caving follows. Three methods of operating wells have been employed—the "Tully plan," "the Detroit plan," and "the Trump plan." Both the Tully plan and the Detroit plan involve the formation of the aforesaid conical cavity with constant caving of shale above and deposition of mud on the side wall; the Trump plan was developed to avoid both these circumstances and thus materially prolong the life of a well. Details of the three plans follow. The Tully Plan In the Tully plan, the water passes down the annular space between the casing and the center tube, the brine rising in the center tube (Figs. I and 2). An inverted conical cavity is formed, the side wall of which relatively soon becomes so flat that it is blanketed by mud and impurities from the rock salt; this blanket limits dissolving action to the perimeter of the base of the cone, situated at the top of the saline bed. Caving of the overlying strata follows, and the total production of brine from the well is comparatively small. The Detroit Plan In the Detroit plan, the water passes down the center tube, the brine rising in the annular space between the center tube and casing (Figs. I and 2). Initially, this flow forms a pear-shaped cavity in the bottom of the salt bed, but this cavity soon changes in shape to that of an inverted cone, as under the Tully plan, with the attendant disadvantages inherent in that plan. Application of the Detroit plan is limited to salt beds 300 ft. thick as a minimum. This depth of bed is necessary to prevent fresh water of lower specific gravity than the brine from rising in the

Jan 1, 1948