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By B. P. Nutter, M. Lebourg, J. A. McAlister

The Multi-Flow Evaluator (MFE) is a new system of tools providing an original approach in drill-stem testing. It improves control during the testing operation and gives a more accurate evaluation of the fluid recovered while providing additional pressure information for reservoir analysis. The tools are operated entirely by up and down motion of the drill stem. This up and down operation provides a positive means of control and offers easily observed surface indications of tool operating position. An unlimited number of shut-in and flow periods may be taken with this tool while in the hole. The key to the success of the MFE system of tools is the safety seal packer. Until this development, operation of the tools by up and down motion only had proven unreliable. The success ratio of the MFE now exceeds the ratio achieved by conventional tools. The equipment includes a 2,750-cc chamber in which a representative sample of the flowing formation fluid is trapped at the end of the last flow period and brought to the surface under pressure. The sample can be evaluated at the wellsite or transferred under pressure for laboratory analysis. The sampling feature of the tool allows a sample to be obtained from a reservoir which has suffered minimum influence from production. A representative sample can be obtained for laboratory or empirical analysis by employing a testing technique to minimize drawdown during flow periods. Interpretation methods to take advantage of this additional information are presented and supported by actual field examples. INTRODUCTlON The Multi-Flow Evaluator (MFE) represents the most recent technical advance in formation testing. Drill-stem testing techniques prior to the MFE have been limited in three areas—(1) operaiion, (2) recovery analysis, and (3) reservoir analysis. The tools in the MFE system allow maximum control during testing and provide test information superior to that obtainable with conventional tools. The system of tools and the operation procedures are described to illustrate the mechanical advantages over present tools. Methods of pressure build-up and fluid

Jan 1, 1966

By Lawrence S. Darken

STAFF: Editor, Gerhord Derge Cornegie Institute of Technology Schenley Pork Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: J. S. Smart, Jr., President; C. C. Long, Past-President; K. L. Fetters, Vice President; T. D. Jones, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: C. L. McCabe, Chairman; H. L. Bishop, K. L. Fetters, J. J. Harwood, W. A. Krivsky, F. C. Longenberg, R. E. Lund, W. 0. Philbrook, L. L. Seigle, R. L. Smith, and F. L. Vogal. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: C. L. McCabe, Chairman; R. E. Lund, Vice-chairman; D. H. Baker, Jr., W. A. Krivsky, R. A. Lewis, Paul Qusneau, A. S. Russell, R, E. Shinkoskey, W. W. Stephens, and M. E. Wadsworth. Institute of Metals Division: L. L.Seigle, Chair-man, P. A. Back, J. J. Backer, l.l. Bessen, J. 0. Betterton, Jr., J. 8. Clark, R. S. Davis, A. E. Dwight, R. W. Fountain, R. B. Gordon, C. D. Graham, Jr., R. W. Guard, J. C. Gurland, E. L. Harmon, J. J. Hager, A. A. Hendrickson, M. Harmon, J. N. Hobstatter, H. H. Johnson, Jr., H. 5. Kolish, R. R. Nash, T. N. Rhodin, R. H. Richman, W. Rostokar, P. G. Shawmon, C. W. Spencer, L. Slifkin, J. K. Stanley, C. D. Starr, R. Steinitz, and H. C. Stumpf. Iron and Steel Division: H. L. Bishop, Chairman; 2. E. Boni, F. C. Langenberg, J. B. Wagstaff, and T. V. Wainwright. Published bimonthly by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription PetroleumEngineers,$30 per year for non-AIME members in United States and North, South, and Central America; 332, foreign; $5 for AlME members. Single copies, $4.00, single copies foreign, $5.00. The AlME is not responsible for any statement mode or opinion expressed in its publications . . . Copyright 1%1 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address; AIME New York ..Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts.. .Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 221, Number 4.

Jan 1, 1962

By Thomas C. Wilder

Jan 1, 1965

Jan 1, 1970

By L. E. Fish, G. S. Wyman

CHUQUICAMATA open-pit mine is capable of producing a total of 105,000 tons daily. When the sulphide plant is operating to capacity the distribution of this quantity will be approximately 30,000 tons sulphide ore, 30,000 tons oxide ore and 45,000 tons of waste. At that time the combined capacity of the oxide and sulphide plants will be about 540 million lb of copper per year. Twenty one benches have been opened to date and all are still active except the three top ones at the northeastern limit of the pit. These have been pushed back to final slope line. The pit is 8850 ft long, 3540 ft wide and 980 ft deep. Benches are not all developed to a standard height as the large development shovels used in cutting new benches have been of different size and range. At this time new benches 521 ft high are being developed with an' 11-yd shovel. Ore haulage through the greater part of the pit operation has been on down grades to the crushing plant. With the opening of bench F-4 in April 1944 the first adverse-grade ore haul was encountered. Of the total tonnage now being mined, 35 pct comes from the four benches that are below the level of the crushing plant yard. Waste had been dumped on the same or nearly the same level as the bench from which it was removed up to the opening of bench F-4. Waste from this and lower levels is hauled to the level of the crusher, yard where it must cross the flow of ore traffic to reach the only available dumping space to the east of the mine. The average ore haul is 3.13 miles one way shovel to crusher, and the average waste haul from that portion handled by railroad is 3.32 miles one way from shovel to waste dump. Waste that is being removed by truck haulage from the upper part of the -mine is hauled an average of 1 mile. Ore loaded by trucks is hauled 3/4 mile to a car loading ramp and then by rail to the crushing plant. Drilling and Blasting There are two types of development for blasting being used: One for opening new benches and the other for bank shooting. The former consists of 9a in. diam churn-drill holes drilled 11.8 ft center to center in rows 10.2 ft apart with the holes staggered in the rows thus giving an equilateral-triangle pattern of 11.8 ft on a side. After the first block, 492 ft long by 71.5 ft wide, is shot in the pattern described above, the cut is advanced by smaller shots consisting of four rows of holes spaced 23 ft center to center with the rows 23 ft apart. These shots are fired in conjunction with side shots in which the holes are drilled 33 ft center to center and 29.5 ft back from the toe, thus squaring up the bank for subsequent shooting. An average bank shot consists of about 60 holes drilled in two rows parallel to the face, 30 holes to

Jan 1, 1952

By R. Schuhmann

Jan 1, 1965

By FRABK HERVEY PETTINGELL

THE stock exchange and its functions is about as well understood by the average individual as the fourth dimension. What is a stock exchange? Divested of the rules and regulations by which it is governed, and the facilities it provides for the convenient handling of securities, it would be in its nude state nothing more or less than a meeting place for brokers. The stock exchange in America dates back to 1752, when a group of merchants of New York established a meeting place at the foot of Broad Street for the purpose of dealing in meal and slaves. The first definite orgarization, however, had its beginning in 1792 when 24 New York brokers signed an agreement not to buy or sell public stock for less than one quarter per cent. commission. From this small group has grown by gradual degrees, the greatest organized security market in the world, namely, the New York Stock Exchange. At the present time there are 27 stock exchanges in the United States and 5 in Canada. Based on the volume of business transacted, the Los Angeles Stock Exchange ranks 6th among them. This is attributable to the fact that strictly speaking Los Angeles has never been a stock exchange town, like some other large cities. Take for instance San Francisco, which supported one stock exchange from 1862 to .1882 and has since supported two. No city, by the way, should tolerate two stock exchanges at the same time. It is an economic folly and a senseless duplication that can be compared with rival telephone companies or competing street railway systems, paralleling each other's lines and always leads to trouble and confusion, and sooner or later one or the other falls by the wayside. While Los Angeles has had stock exchanges of one kind or another since 1896, none of them attracted much attention until 1899 when the present exchange was organized and it did not get well under way until along in 1906.

Jan 1, 1925

By R. E. Radabaugh, J. M. Brown, J. S. Merchant

The Gilman district is on the northeast flank of the Sawatch Range in central Colorado. It has yielded a total of 10,000,000 tons of ore having a value of over $250,000,000. Paleozoic sediments intruded by a Tertiary quartz latite sill and unconformably overlying Precambrian intrusives and metasediments comprise the country rock of the area. The sediments strike northwesterly and dip 8° to 12° northeasterly. Structures in the Precambrian are related to the Homestake shear zone of the Colorado mineral belt. Only minor folding and faulting occur in the sediments. The principal ore bodies are massive sulfide replacement deposits in carbonate rocks. They consist of long, pipe-like mantos in the completely dolomitized Mississippian Leadville Limestone and funnel-shaped chimneys of copper- silver ore cutting across the Mississippian and Devonian strata. Mineralization is continuous from the chimneys into the mantos. The principal ore bodies are roughly in the shape of a four-tined fork which points up dip. Smaller manto deposits occur in the Cambrian Sawatch Quartzite, and fissure veins are present in the Precambrian rocks. The principal minerals in the mantos are marmatite and galena in a gangue of pyrite and manganosiderite. The chimneys consist of a central core of pyrite with erratically distributed chalcopyrite, tetrahedrite, freibergite, and occasional galena with a shell of zinc ore on the outer margin. Both the chimneys and the mantos are surrounded by imperfect shells of manganosiderite and sanded dolomite. The mineralization is of Laramide age. Hydrothermal alteration affects all rock units to varying degrees. Clay mineral alteration halos occur around the ore bodies. Hydrothermal solutions have developed sanded rock, rubble filled channels, and banded zebra textures, principally in the Leadville Limestone. Structural control of the ore bodies is not well defined. Both the location of the district and the chimneys are probably related to basement structures. The mantos are largely controlled by stratigraphic factors and a pre-Pennsylvanian karst topography in the Leadville Limestone, which were modified by hydrothermal activity, and by weak zones of northeasterly trending faults.

Jan 1, 1968

By EDWARAD A. SIVEDENBORMG

REPORTS have been made at different times on the progress of water encroachment in the Frontier sands in the Salt. Creek oil field, Natrona county, Wyoming. All previous reports have, -however, been largely based on the position of water in the sands as determined by various physical tests. Subsequent information has been secured through a preliminary investigation of the porosity, grain size and degree of saturation of the Frontier sands. Also, a closer differentiation has been made between the waters encountered incident to the production of oil by means of chemical analysis. In view of the more recent developments there has been a need of a water encroachment map of the first Wall Creek based on a field survey and additional information acquired since the water encroachment map of the sand of 1926, by J. S. Ross and E. W. Henderson, petroleum engineers of the U. S. Geological Survey. The present report is confined to a study of the first Wall Creek sand and was written in connection with the preparation of the map, showing water encroachment in this sand. The first Wall Creek sand was the discovery sand in the field, the first well having been drilled in 1908. Its thickness averages 120 ft. and, varies between 90 and 160 ft. The sand is in the Colorado group of the Upper Cretaceous series and is further considered as a part of the Frontier formation found in other parts of Wyoming.

Jan 1, 1930

By Donald F. Hammer, Donald W. Peterson

The Magma mine at Superior, Arizona, has produced over 13 million tons of ore yielding 1.5 billion pounds of copper. It is a mesathermal deposit, and, although the bulk of the ore has come from the Magma vein, most of the recent production has come from replacement deposits in limestone. The mine lies in a Precambrian and Paleozoic sequence of rocks that includes schist, diabase, quartzite, shale, and limestone; nearby, these rocks are intruded by igneous bodies of Mesozoic age that were probably the source of the ore-bearing fluids. Locally, these rocks are overlain by Cenozoic volcanic rocks and conglomerate. Layered rocks at the mine dip eastward about 30°. The area is extensively faulted, and surface faults are grouped into an earlier east-trending set and a later northtrending set. An additional set of diagonal faults that trends northwest and northeast is recognized underground. The east-trending Magma vein-fault, with its splits and branches, is the principal mineralized structure of the district. The bulk of the ore occurs in large ore shoots that plunge steeply westward and are sporadically connected by irregular ore shoots dipping gently eastward. The main ore controls apparently are selective zones of permeability related to the transverse faults. A bed of crystalline limestone near the base of the Martin Limestone (Devonian) is the host for the replacement ore bodies-discontinuous tabular pods dipping eastward parallel to the bedding. Selective permeability is again the apparent ore control, caused both by local hydrothermal solution of limestone and by deformation along faults. The principal copper minerals in the vein are chalcopyrite, bornite, enargite, tennantite, chalcocite, and digenite; these minerals vary in abundance according to a distinct zoning pattern. The upper part of the mine yielded considerable zinc as sphalerite, and the oxidized zone was rich in silver. The chief gangue minerals are pyrite, quartz, and hematite. In the limestone replacement bodies, chalcopyrite and bornite are the chief ore minerals.

Jan 1, 1968

By John R. Freeman

THIS paper relates entirely to the casting of brass under fluid pressure in steel dies Die castings of metals and alloys of low melting point have been available for many years but the development of brass die castings has been relatively recent, occurring within the past five years The successful development of brass die castings has resulted from the availability of alloy steels that would give satisfactory life as dies and the development of suitable die-casting machines The melting point of copper is 1084° C (1983° F ) and of a high brass about 900° C (1652° F ), as compared to 327 5° C (6215 °F) for lead, 419 4° C (786 7° F) for zinc and 658 7° C (1217 7° F) for aluminum, temperatures that ale indicative of the casting temperatures required for the various types of alloys, of which the melting points are somewhat lower than those of the pure metals TYPE OF DIE-CASTING MACHINE In the well-known plunger and gooseneck types of die-casting machines used for casting the alloys of relatively lower melting point, much of the working mechanism is immersed in the molten alloy For alloys having the relatively high melting point of brass, this obviously is impossible Machines with a separate melting chamber are essential Two rather distinct types are in extensive use at the present time, the Pack and Polak machines, the former designed by Charles Pack and developed at the American Brass Co , the latter developed by Zoseph Polak, of Prague, Czechoslovakia The principles of operation of these machines have been described in articles by Pack1,2,3 and by Sieg 4

Jan 1, 1935

Jan 1, 1964

By Fred H. Perfect

The thermite process, now approximately 80 years old, has heretofore been practiced in ceramic vessels. This paper outlines the successful production of several million pounds of alloy produced in zuater-cooled copper vessels. THE high temperatures necessary to produce fluid high-alumina slags have probably discouraged earlier workers from attempting to utilize water-cooled vessels. The following is a report of the successful application of this method, together with a report of the physical and chemical problems which had to be solved to make the process practical. About 1955, when Reading Alloys was more concerned with the production of ferrotungsten than with most other types of alloys, it was found to be exceedingly difficult to predict the reaction rate that one would experience from one tungsten ore to another . This difficulty was increased for two reasons: the physical state of the ore as received was seldom uniform, and the size of the mass to be reduced is a very important factor in developing the proper mix for the final reaction rate and temperature. For example, the reduction of ferric oxide with aluminum would theoretically produce temperatures of about 2600°C, and, in spite of the losses due to radiation, the energy is quite sufficient to produce a very fluid slag and iron effecting a very clean separation. On the other hand, the reduction of ferrous oxide with aluminum, while it is not as energetic as the first reaction, nevertheless should give temperatures above 2000"C, which should cause separation of alumina and iron, but, in practice, this is not the case and good fluid slag is not obtained. The heat of reaction, calculated from the thermo-dynamic heats of formation of the constituents of the reaction, offers a convenient guide to the feasibility of a thermite reaction. Thus, the values listed in Table I can be used as an approximate guide for estimating the results which may be expected in the reduction of various oxides and combinations of oxides using aluminum as the reducing agent. As a generalization, those reactions releasing approximately 600 cal per g of total mass represent the lower limit at which to expect separation of slag and metal. On the other hand, those reactions which release 1100 to 1200 cal per g are too violent to be used successfully without the addition of considerable inert material, such as lime, fluorspar, and so forth. Reaction rate is also a very important factor. This, of course, is governed very largely by the sizing and intermingling of the oxidant and reductant and by the starting temperature of the reactants. This is why those figures shown in Table I can only be a general guide. Further, it must be understood, that by adding powerful oxidizing agents, such as nitrates, chlorates or metallic oxides, such as molybdenum trioxide or chromium trioxide, certain problems respecting low temperatures are not necessarily solved. This is true in the addition of oxidants, such as sodium chlorate. By adding too high a concentration of sodium chlorate as a booster for a particular reduction, explosions are generated. Generally, they are of an intermittent type so as to give a Roman Candle effect to the reduction itself; with each surge resulting from a minor explosion more and more material is thrown

Jan 1, 1968

By M. F. Trice

PYROPHYLLITE is a hydrous aluminum silicate (A12Si4010(OH)2)1 that occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mobs' scale.1 The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey,2 contain pyro-phyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, "are noticed in but small quantities to the extent they might occur as accessory constitu-ents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 percent and the alumina from 22 to 33 percent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent.

Jan 1, 1940

By A. S. Argon, G. East

From their study of the anisotropy of grain boundary mobility in aluminum, the authors conclude that tilt boundaries have a higher mobility than twist boundaries because the atomic misfit at the pure-twist boundary is relatively small compared to the misfit at a tilt boundary for a given amount of misorientation. If this is true, then one would expect a twist boundary to have a lower grain boundary energy than the corresponding tilt boundary. Fig. 6, taken from the work of Gjostein and Rhines,10 shows that this is indeed the case for [001]-cu tilt and twist boundaries in the high-angle region, thus lending support to the authors' conclusion.

Jan 1, 1968

By T. G. Sieber, T. D. Tiemann

The extraction of quartz from siliceous iron ores by dissolution in sodium hydroxide solution has been described in detail in AIME Transactions. l923 data reported covered the temperature range from 230-416°F, where a continuous increase in the amount of silica extracted with increase in temperature was found. It is the purpose of this paper to describe some unexpected results of more recent work exploring principally the range of 500600°F where higher rates and greater amounts of silica extraction were antici-p ted. In brief, the experimental procedure consists in digesting the ore under pressure in solutions of sodium hydroxide, filtering the suspension and weighing and analyzing the dried residue for iron content. The amount of extraction is calculated from the weight loss or from the iron analysis of the residue and that of the original ore.

Jan 1, 1969

By John Freeman

THIS paper relates entirely to the casting of brass under fluid pressure in steel dies. Die castings of metals and alloys of low melting point have been available for many years but the development of brass die castings has been relatively recent, occurring within the past five years. The successful development of brass die castings has resulted from the availability of alloy steels that would give satisfactory life as dies and the development of suitable die-casting machines. The melting point of copper is 1084° C. (1983° F.) and of a high brass about 900° C. (1652° F.), as compared to 327.5° C. (621.5° F.) for lead, 419.4° C. (786.7° F.) for zinc and 658.7° C. (1217.7° F.) for aluminum, temperatures that are indicative of the casting temperatures required for the various types of alloys, of which the melting points are somewhat lower than those of the pure metals.

Jan 1, 1935

By J. D. Rice, S. C. Pitzer, C. E. Thomas

Interpretation of pressure build-up data obtained in the conventional manner has often been difficult because of the deviation from theoretical behavior. Major causes of this deviation have been attributed to damage and afterflow, and to fluid redistribution in the wellbore which, in extreme cases, can result in a pressure hump in the early portion of the build-up curve. Theoretical investigations show that bottom-hole pressure is definitely influenced by phase redistribution in the tubing column during surface shut-in tests, and that the magnitude of the effect is sensitive to the producing gas-oil ratio and stabilized rate of flow in the well. For field experiments a wire-line tubing packer, which can be run in the tubing against a stabilized flow rate, was developed for bottom-hole shut-in tests. By use of this bottom-hole .shut-in method, pressure humps previously observed in surface shut-in tests were completely eliminated and the effects of afterflow minimized. Analog and digital computer studies have been made to obtain theoretical curves for comparison with field curves, and remarkable agreement between the results of bottom-hole shut-in tests and theoretical curves has been obtained. INTRODUCTION Pressure build-up data from shut-in wells have been used by the petroleum industry to determine the permeability of the formation, to estimate wellbore damage, to evaluate the static reservoir pressure and to speculate reservoir volume. Calculation of these factors is based on methods of analysis developed for theoretical systems whose build-up curves have a charac- teristic shape when the wells are shut-in at the sand faCe.1,2,3,5,8,10 However, field curves obtained by conventional surface shut-in methods do not always exhibit this characteristic. Such factors as stratification, rock heterogeneities and irregular reservoir geometry can cause the character of a build-up curve to deviate from that predicted by theory for a simple system. In addition, all field build-up data are affected by the methods utilized in obtaining the measurements. Conventional surface shut-in techniques allow two effects to occur which contribute directly to the manner in which pressure builds up at the sand face. The first, afterflow, has been recognized for some time and methods are available for estimating the magnitude of its effect and for correcting its influence.' The second, phase segregation in the tubing column after shut-in, has been reported only recently and appears to exert a considerable influence on the character of field build-up curves.!' In extreme cases, phase segregation can produce "pressure humps" in the early portion of the build-up curve. Such curves have been considered anomalous and have defied analysis. It is the purpose of this paper to discuss the effect of phase segregation in the tubing string during build-up and to present a bottom-hole shut-in technique for obtaining field build-up data which minimizes the influence of afterflow and eliminates phase segregation effects. It will be shown that reliable reservoir information can be calculated from build-up measurements obtained using this method, even though conventional surface shut-in tests on the same wells yield anomalous data. DISCUSSION OF PHASE REDISTRIBUTION EFFECTS Some of the effects of phase redistribution on pressure build-up curves have been described previously by Matthews and Stegemeier" who have presented evidence that phase segregation is responsible for the pres-

By Frank W. Dickson, George Tunell

Five hot spring areas of the western United States show evidences of present day deposition of HgS; two also show evidences of accompanying Sb2S3 deposition. Sulfide minerals are depositing at or near the surface from hot waters that differ for each spring ai:ea in amount and kinds of dissolved matter. All the springs contain dissolved substances that act as buffering agents and that cause increased alkalinity with increasing temperature. Transport of Sb2S3 is possible in H2O and in boron and sulfide solutions. Increasing alkalinity and temperature enhance stibnite solubility. Quantitatively important transport of HgS appears restricted to alkaline sulfide solutions that contain HgS2=. Elemental mercury probably forms in deep hot waters because HgS breaks down into mercury and sulfur above 200°C, and free S is removed by reaction with water. Elemental mercury should accompany HgS2= in solutions that were at 200°C or higher. Cinnabar deposits from saturated alkaline sulfide solutions because of combinations of temperature decrease, dilution, oxidation, and reactions with wall rock: Amedee Hot Springs, Boiling Springs, and Coso Hot Springs are areas in which HgS is the only sulfide deposited. Hot waters at Amedee and Boiling Springs are supersaturated with HgS or transport colloidal HgS. Steamboat Springs waters deposit mainly silica and stibnite, but they have deposited HgS recently. Sulphur Bank waters deposit mostly stibnite and some HgS. The hot-spring waters of all springs represent highly modified deep water. Field and laboratory studies support the concept of transport of HgS in moderately alkaline sulfide solutions as HgS2=. Fluctuating deposition of stibnite and cinnabar reflects availability of sulfide or variations in deep-source HgS and Sb,S,. Silica and HgS dissolve mutually in alkaline sulfide solutions, and cinnabar and quartz would be expected to deposit simultaneously. Free mercury given off by hot-spring waters would impregnate country rocks.

Jan 1, 1968

By R. M. Waterstrat

X-ray diffraction and metallographic examination of binary Mn-rich alloys with Ti revealed the presence of intermediate phases in this system. A binary R phase has been identified and also a phase having an a-Mn type structure. The X-ray pattern of the phase TiMn3 is presented and a tentative phase diagram for the Mn-rich portion of this binary system has been constndcted. MANGANESE-rich alloys with titanium have been subjected to thermal analysis at temperatures down to 1100°C by Hellawell and Hume-Rothery.1 Their results indicate the existence of an intermediate phase TiMn3 in this binary system. This phase appears to coexist with the Laves phase TiMn2, and with terminal solid solutions based on the allotropes of manganese, at least down to 1100°C. The above investigators did not attempt to determine the crystal structure of this phase, however. Since, by analogy to the binary systems Mn-V and Mn-Cr3 one might expect to find a phase in this region of the diagram, it seemed desirable to obtain X-ray diffraction patterns of alloys in the concentration range in question, in order to ascertain whether the sigma phase or related structures occur. EXPERIMENTAL PROCEDURES Alloys were prepared by arc-melting electrolytic manganese and iodide titanium in a water-cooled copper crucible under a helium atmosphere. Excess manganese was added to each melt in order to allow for losses incurred during melting. The alloys were then wrapped in molybdenum foil and sealed in evacuated quartz tubes for annealing at various temperatures, as shown in Table I, followed by quenching in cold water. Although the inside of the tubes showed evidence for some loss of manganese from the specimen during annealing, there was no evidence of any reaction between the specimen and either the molybdenum foil or the quartz tube at these temperatures. It was later found that the manganese loss was considerably reduced by annealing these alloys in sealed quartz tubes containing one atmosphere of purified argon. As an added precaution the surface of each specimen was ground off before crushing the alloys to -270 mesh powder, using a hardened steel mortar and pestle. X-ray powder patterns were obtained using either FeKa or CrKa radiation in an asymmetrical focusing camera, which gave excellent dispersion of the closely spaced lines. Pictures were also obtained using a Debye camera of 5-cm radius which provided data in the angular region not covered by the focusing camera. The alloy specimens were polished and examined metallographically, using an etchant consisting of 60 pct glycerine, 20 pct nitric acid, and 20 pct hydrofluoric acid. The 10-g buttons were in each case broken in half and found to be well-melted and free of any gross segregation. One half of certain alloy buttons was submitted to chemical analysis in the "as-cast" condition. No appreciable change in composition seemed to occur during annealing . RESULTS The X-ray pattern of alloy Ti1.17Mn0.83 was found to agree well with that of the ternary R phase which was first found in the Mo-Cr-Co system,' and re-

Jan 1, 1962