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By H. E. McKinstry

Movement on a fracture of irregular shape can cause local widening of the fissure and thereby offer freer channelways for circulation of ore-depositing solutions. This influence: coupled with large areas of wall rock available for reacting with ore solutions in brecciated and shattered ground can account for locally active deposition of metals and the resulting ore shoots. Such irregularities in the fracture system may be caused by local variations in the strength of rocks and by pre-existing lines of weakness, especially if these stand at favorable angles to certain components of the fracturing stress. Therefore correct interpretation of the mechanics of fracturing should permit deductions as to structurally favorable places on unexplored portions of the vein system. Introduction It has long been recognized that movement on a curved or irregular fault surface is capable of separating the walls in certain portions of the fault, but until very recent years the importance of this mechanism as a factor in localizing ore shoots has escaped proper recognition. A short time ago W. H. Newhouse' presented a careful analytical study of displacements and their corresponding open spaces. For reasons that will be discussed later, it frequently happens that portions of the vein which are favorably oriented are not merely wider but also richer than the average. In many cases the widening with its accompanying richness coincides with very minor changes in the dip or strike of the vein, irregularities that commonly escape notice unless the vein is mapped in detail and a careful geometrical analysis made. While the relationship between the width of the vein and the changes in dip or strike has been recognized as a matter of observation, the irregularities have been accepted as more or less the result of accident. There has been very little effort except in isolated cases to find out the causes of these changes in dip or strike. Yet it is clear that if the causes can be recognized and expressed in terms of geologic structure the geologist will know where to look for repetitions of these favorable conditions either on extensions of the same vein or on adjoining veins. Any lack of understanding of the causes is due to the limitations of our ability to interpret our observations and not to the sheer capriciousness of

Jan 1, 1941

By L. W. Strock

Metallurgists handling lead and zinc ores have long been familiar with the spectrograph as a routine analytical tool, as its earliest regular use by American industry was in controlling impurities of zinc metal and its alloys. This application has been extended to other metal industries on an extensive scale, accompanied by refinements of procedure to such an extent that a large part of some metals produced, especially magnesium, aluminum and steel, are checked only by spectrographic methods for conformity to specifications. The spectrographic analysis of ores and other poorly conducting powdered solids presents difficulties not encountered with metallic samples, which can be arced or sparked as self-electrodes or can be readily dissolved, so that their solutions can be analyzed, as in the American Society for Testing Materials standard methods for zinc and zinc-base alloys. Spectra of powdered solid samples can be prepared by using carbon electrodes provided with a crater of suitable size, into which the sample is packed. Ore samples and many other powdered solid materials usually analyzed in the chemical and metallurgical laboratory are more complex and varied in composition than samples of metals produced in large tonnages. 'lore preliminary work therefore is usually necessary in devising a spectrographic method for analyzing a given type of powdered sample than for analyzing metal samples, in order to use that method with confidence. The howledge that the standard samples and unknowns produce equivalent line intensities at equal concentration is the fundamental basis of any quantitative spectrographic method. On the other hand, powdered samples have an advantage over metals in that any desired number of chemical compounds can be mixed dry in any desired ratio to produce a synthetic standard. Expcrience has shown, however, that spectra of elements in finely divided compounds introduced into a standard in preparing a synthetic ore sample do not always behave in the electric arc in a manner that produces spectral line intensities similar to those observed at the same concentration in a natural mineral. In ore samples minor elements frequently are contained in the crystal lattice of larger particles of an abundant ore mineral. Their dissociation and volatilization from the sample into the arc then proceeds differently in the standard and sample, with resultant differences in intensity. During the past 10 years I have devised and applied several quantitative spectrographic methods for determining various elements in rocks and minerals in connection with studies on their geochemistry,' but the incentive has gradually changed since the summer 0. 1940 to the specific practical problem of searching for domestic sources of rare and stratcgic metals. The

Jan 1, 1949

By H. N. Hall

Various factors must be considered in an engineering evaluation of gravity-drainage reservoirs. Among these are: (1) the effect of producing rate on total oil recovery; (2) the effect upon well productivity and ultimate recovery of the pressure level maintained during the producing life of the reservoir; (3) the economic advantage of full or partial pressure maintenance; and (4) estimate of the rate of gas production and injection and the possible purchase of gas under conditions of full pressure maintenance to ascertain compressor facilities needed. All of these factors can be evaluated only when a reliable method is employed for determining reservoir performance in gravity-drainage reservoirs. The purpose of this paper is to present a general method for calculating the performance of a gravity-drainage reservoir. This method is applicable for conditions of complete pressure maintenance, partial pressure maintenance and normal pressure depletion. Provisions are made to take into account variations throughout the reservoir of reservoir configuration, changes in permeability and fluid composition. Based on the method presented in this paper, an IBM 650 computer program has been developed. The past performance of an actual gravity-drainage reservoir producing under conditions of declining pressure and no gas injection was duplicated using this program. INTRODUCTION In tilted reservoirs the production of oil is influenced by drainage of oil from upstructure to downstructure locations. When this downstructure drainage of oil is sufficient to cause effective segregation of the gas and oil in a reservoir, the reservoir is usually classified as a segregation drive or gravity-drainage reservoir. (Discussion will be restricted to gravity-drainage reservoirs which have no encroachment of edge water.) The important feature in gravity-drainage reservoirs is the density difference between reservoir oil and gas. These phases tend to segregate in the reservoir with the result that in the gas cap the oil saturation is maintained at a higher level by drainage of oil from the gas-cap area. Oil can be produced from the oil zone at a low gas-oil ratio and reservoir energy is thereby conserved. The standard material balance in not adequate for predicting gravity-dramage reservoir performance because it does not take into account the difference in saturation above and below the gas-oil contact. Several authors'.' have presented methods for calculating the performance of gravity-drainage reservoirs in which reservoir pressure is maintained constant by gas injection into the gas cap. Using some simplifying assumptions, these methods can be employed with a desk calculator to give acceptable results. The problem of predicting the performance of gravity-drainage reservoirs under the conditions of declining reservoir pressure is many time more complex than that of constant pressure. fierefore, attempis to develop a method suitable for desk calculation have required excessively simplified assumptions. In the past several years, highspeed digital computers have become more widely available for reservoir engineering problems. These corn puters are well suited to problems such as the prediction of the performance of gravity-drainage reservoirs with pressure decline. Many of the simplifying assumptions necessary for hand computation can be eliminated so that a realistic approach to the gravity-drainage process can be made. CONCEPTUAL PICTURE OF OIL MOVEMENT IN GRAVITY-DRAINAGE RESERVOIRS Before attempting to develop an analytical treatment for conditions occuring in a gravity-drainage reservoir, a concept should be formed concerning the movement of fluids in the reservoir as oil is produced. A review of the literature'.' shows that it is customary to classify gravity-drainage operations into two categories—(1) with complete pressure maintenance, and (2) with declining pressure. The same line of reasoning will be followed in presenting the concept of the movement of fluids in the reservoir because it is easier to visualize the movement of fluids under conditions of complete pressure maintenance. After discussing complete pressure maintenance, an analogy will be made between that and the case of declining pressure. It should be kept in mind throughout that the final aim for the problem of solving gravity-drainage performance with digital computers will be to develop a general program for any kind of gravity-drainage reservoir. COMPLETE PRESSURE MAINTENANCE One feature which is generally common in gravity-drainage reservoirs is a gas cap located at the top of the structure. This is shown in Fig. 1(a). Fig. l(b) shows oil saturations that might occur through the reservoir. In the gas cap, oil saturation is lower than

By C. Norman Cochran, James L. Brandt

ALTHOUGH gas in aluminum and its effect on aluminum products have been the subject of a number of papers, not many quantitative determinations of the hydrogen content of solid aluminum and its alloys have been recorded in the literature. For solid aluminum samples, four investigators have reported hydrogen contents which appear reasonable compared with the hydrogen solubility of 0.7 ml per 100 g, STP, in molten aluminum at 660°C established by Ransley and Neufeld' and verified by Opie and Grant' and Ransley and Talbot. Sloman," who used a vacuum fusion procedure, reported the hydrogen content of some high purity aluminum as 0.66 ml per 100 g, STP. Griffith and Mallett, employing the tin fusion method, reported the internal hydrogen content of six different aluminum alloys as ranging from less than 0.1 ml per 100 g, STP, for 1100 alloy to 0.7 ml per 100 g, STP, for 4043 alloy (previously 43S, a 5 pct Si alloy). Eborall and Ransley," using a solid extraction of the gases at 600°C, reported hydrogen contents ranging from 0.1 ml per 100 g, STP, to 1 ml per 100 g, STP. Ransley and Talbot reported that several thousand analyses on 99.2 pct and higher purity aluminum as well as Duralumin type alloys indicated hydrogen contents ranging from 0.1 ml per 100 g, STP, to 0.5 ml per 100 g, STP.

Jan 1, 1957

An informal discussion on the application of physical chemistry to steelmaking was held during the Annual Meeting of the Institute in February, 1929. Alexander L. Feild presided. In opening the session, Mr. Feild said: We are all familiar with the cooperative mining and metallurgical studies that were begun in 1920 by the U. S. Bureau of Mines, the Carnegie Institute of Technology, and the Mining and Metallurgical Advisory Boards, and in particular with the work on the physical chemistry of steelmaking which was launched under the technical direction of Dr. C. H. Herty, Jr., in May, 1926. It was this work at Pittsburgh more than anything else that was the immediate cause of the formation within the Institute of a committee on the physical chemistry of steelmaking. During the latter part of 1927 a small group of Institute members interested in. the general subject of the physical chemistry of steelmaking undertook the organization of a subcommittee within the Iron and Steel Committee, to foster an active interest in this comparatively new field among the Institute membership and to obtain papers for publication in the Transactions, covering the various phases of the general subject. This plan was conceived by C. E. Meissner, to whose active efforts at the outset as well as during the past year is largely due whatever measure of success the plan has thus far attained. The subcommittee, now a committee of the Iron and Steel Division, was recognized and formally made a part of the Institute's organization at the February, 1928, meeting. As originally organized and as const,it,uted during the past year the committee has been made up as follows: C. H. Herty, Jr., C. D. King, A. B. Kinzel, John Johnston, C. E. Meissner, L. F. Reinartz, R. B. Sosman, and A. L. Feild, Chairman. Dr. C. H. Herty, Jr. has just been elected chairman for the coming year and C. E. Meissner has been reelected as secretary. From the outset it has been the settled policy of the committee to make membership an annual rather than a permanent matter and to reconstitute in part the membership of the committee each year by dropping a certain number of members and adding new members. In view of the fact that the work of the committee is still in a

Jan 1, 1929

By E. V. Daveler

THE milling plant of the Alaska-Gastineau Mining Co. is located at the town of Thane, Alaska, on Gastineau Channel, 4 mi. south of Juneau and directly across the channel from the Ready Bullion mine of the Treadwell mines on Douglas Island. Previous to the organization of the Alaska-Gastineau Mining Co., in 1912, the milling was done at the stamp mill of the Alaska Perseverance Co. located at the mine in Silver Bow Basin. But the contemplated increase in production made it necessary to locate the mill on Gastineau Channel, as not enough water was available at the mine during the winter months, nor was there room for taking care of the large tonnage of tailings that would ultimately be discarded from the mill. CHARACTER OF ORE The gold and silver values occur in quartz lenses associated with pyrrhotite, galena, arsenical pyrites, and zinc blende. These lenses occur in large bodies of slate, schist, and metagabbro, which also carry some valuable metallic contents. With the essential low cost of mining, it was necessary to mine large bodies of low-grade material containing the high-grade streaks. Of the minerals, pyrrhotite, the magnetic sulfide of iron, is predominant, and galena is the next sulfide present in quantity. The gold occurs free and coarse and associated with the iron sulfide in its finer state. The silver occurs with the lead or is alloyed with the gold. A chemical analysis of the ore shows Silver 0.10 oz. Magnesia 0.4 per cent. Silica 59.7 per cent. Sulfur 1.2 per cent. Iron 5.2 per cent. Lead 0.1 per cent. Alumina 21.4 per cent. Zinc 0.2 per cent. Lime 5.0 per cent.

Jan 1, 1920

By G. W. Healy, W. D. Forgeng, N. R. Griffing

The liquidus surface of the C-Cr-Fe system to 1900°C has been mapped from carbon solubility and freezing point measurements, metallographic observations, and published data. In the graphite field, the surface drops precipitously to meet a slope descending from the Cr3C2-C join through the mixed carbide fields to a meandering eutectic valley; this flows from the Cr-C to the Fe-C edge. On the low-cavbon side of the valley, the surface rises to the chromium corner. 1 HE purpose of this inquiry was to gain a more complete knowledge of the C-Cr-Fe liquidus surface. This required an extensive study of carbon and chromium-rich alloys which, in the past, have received the least attention. Sanbongi el al.1 measured the solubility of carbon in liquid alloys containing up to 25 wt pct Cr at temperatures of 1460" and 1545°C and found that it increased with chromium content and temperature. Lucas and wentrup2 also made solubility experiments in graphite crucibles, but at higher chromium contents in the range of 38 to 80 pct and at temperatures of 1550" to 1700°C; however, their experiments were relatively few, and the effect of temperature was not consistent. The present investigation included compsitions ranging from 0 to 94 pct Cr and 1.4 to 11.7 pct C at temperatures up to 1800°C. Saturation experiments in graphite crucibles, thermal analyses during freezing, and metallographic and X-ray diffraction studies were employed to obtain desired information which, together with published data from other investigations about the binary edges and the ternary system at lower carbon levels, made possible the construction of a comprehensive C-Cr-Fe liquidus surface. C-CR-FE LIQUIDUS SURFACE The derived ternary liquidus surface is shown in Fig. 1 where the solid curves are liquidus isotherms. The dashed curves and the binary edges are the liquidus field boundaries of the primary crystals, the arrows along these boundaries indicating their direction with decreasing temperature. Each intersection of three internal boundaries is the composition of liquid involved in four-phase isothermal equilibrium with the three primary crystals whose liquidus fields touch there. It may be observed that a total of six four-phase equilibria occur at melt temperatures. The general topography of the liquidus surface consists of a eutectic valley sloping down from the Cr-C edge at 3.2 pct C to the Fe-C edge at 4.25 pct C. The liquidus surface rises in two directions from the valley, one hillside terminating at the Cr-Fe edge while the opposing hillside rises toward the carbon corner out beyond the top edge of Fig. 1. Both hillsides are interrupted by intersections of surfaces or joints representing the liquid colmpositions of various three-phase equilibria. Seven primary crystals occur, namely a(bcc), ?(fcc), graphite, (Fe, Cr)3C capable of dissolving as much as 15 pct Cr, and three different chromium carbides in which iron is partially soluble by substitution for chromium. The composition ranges of the primary l~hases at melt temperatures are shown

Jan 1, 1962

INTERNATIONAL GEOLOGICAL CONGRESS. (For further particulars apply to the Secretary, 12th International Geological Congress, Victoria Memorial Museum, Ottawa, Canada ; cable address, Geocong, Ottawa.) The Coal Resources of the World.-Three quarto volumes of about 400 pages each, 8 1/4 by 10 3/4 in., and an atlas of about 70 maps in colors, 13 1/3 by 19 1/2 in., bound in heavy paper cover. Edition limited to 3,000 copies, One thousand copies will be reserved for members of the International Geological Congress, and the remainder of the edition will be distributed in the order in which applications are received. Price, $35 per set. Ready in July, 1913. This book is an inquiry made upon the initiative of the Executive Committee of the Twelfth International Geological Congress, with the assistance of geological surveys and mining geologists of different countries, published by: Morang & Co., Ltd., Toronto, Canada. Headquarters During Session at Toronto. The headquarters will be a t the University of Toronto, where there will be a branch post-office open at all hours and at which registered mail may be received or despatched, money orders sent or cashed, etc. A hank will be established at which money may be exchanged. A typewriting service will be maintained, also a telephone service and messenger service. Railway and steamship agents will also be in attendance. A restaurant service providing luncheon in the middle of the day will be arranged.

Jan 8, 1913

By A. R. Troiano, E. A. Steigerwald, F. W. Schaller

The kinetics of crack propagation in a hydrogenated high-strength steel at subzero temperatures indicated that cracking progressed in a discontinuous fashion. The delayed failure process thus involves a series of crack initiations rather than the continuous growth of a single crack. The incubation time required for the initiation of delayed failure was controlled by the diffusion of hydrogen. The activation energy for the process was 9120 cal per g-alom. As the test temperature was lowered the incubation time constituted a greater percentage of the total tinze to fracture, and al -50°F the incubation and fracture times were essentially coincident resulting in instantaneous, catastroplzic fracture. A unique feature of hydrogen embrittlement is the delayed failure process in which the material fails under the action of a sustained load even though it is capable of supporting a higher load for a finite period of time.')' Delayed failure of steel and titanium is characterized by an incubation time, preceding the initiation of a crack in a highly localized region, and the subsequent growth of the crack to ultimate failure.3-5 The kinetics of crack growth in hydro-genated high-strength steels have been studied through the use of resistance measurements and have an important bearing on the mechanism of delayed failure. Delayed failure is believed to be merely a facet of hydrogen embrittlement in which sufficient time is allowed during a test for hydrogen diffusion. The current theories employed to explain hydrogen em-brittlement can be grouped into two types. one6-8 explains the embrittlement on the basis of the pressure exerted by molecular hdrogen in lattice voids or defects while the other9-10 attributes the embrittlement to the influence of hydrogen in the lattice. The mechanism used to explain the nature of the crack kinetics in delayed failure is based on the stress-induced diffusion of hydrogen to the area of maximum triaxiality.3 When the hydrogen concentration in this region reaches a critical value, a crack is nucleated. This initial crack propagates instantaneously until stopped by the higher fracture stress of the adjacent material of lower hydrogen content. The continuation of cracking must then await the further diffusion of hydrogen to the new region of triaxiality near the base of the crack where another initiation will occur. From this mechanism it follows that crack propagation is nothing more or less than a series of initiations with limited fracture. The purpose of this investigation was to examine the kinetics of crack growth in an effort to determine whether or not the process was discontinuous. Studies of crack propagation were conducted at low temperatures to retard the diffusion of hydrogen which is presumed to be the rate controlling process in delayed failure. MATERIALS AND PROCEDURE Specimen Preparation—A commercial heat of air-craft quality SAE-AISI 4340 steel, designated as Heat G, was furnished by the Republic Steel Co. in the form of %-in. hot-rolled bars. The material had the following chemical analysis: Composition of 4340 Steel—G Heat C Mn Si Ni Cr Mo 0,395pct 0.82pct 0.29pct 1.76pct 0.85pct 0.25pct Notched tensile specimens with less than a 0.001 in. radius, Fig. 1, were used throughout the investigation. The specimens were heat treated to a 230,000 psi strength level according to the following sequence: a) Normalize bar stock at 1650°F for 1 hr, b) Stress relieve at 1200°F for 4 hr and furnace cool,

Jan 1, 1960

CONTENTS PAGE SOUTHWARD, GLENN B.-Coal Mining by the V System. Discussed by Glenn B. Southward, Howard N. Eavenson, Edward B. Raiguel, Thomas de Venny, J.. J. Rutledge, Graham Bright 1 ARMS, RAY W.-Dry Cleaning of Coal. Discussed by Ray W. Arms, S. A. Taylor, Howard N. Eavenson, W. R. Crane, F. F. Jorgenson, G. R. Delamater. 6 EAVENSON, HOWARD N.-Data About Labor Employed in Various Bituminous Coal Mines. Discussed by Howard N. Eavenson, George H. Ashley, E. A. Holbrook, S. A. Taylor, R. V. Norris 14 Coal Mining by the V System Discussion of the paper of GLENN B. SOUTHWARD presented at the New York Meeting, February, 1924, and issued as Paper No. 1300-C, with MINING AND METALLURGY, February, 1924. MEMBER.-How do you pay your men for loading? GLENN B. SOUTHWARD.-Everything is on time basis. MEMBER.-How many men do you have loading across one of the diagonal faces? GLENN B. SOUTHWARD.-From four to five, depending on the length of the face. Our loaders are so arranged that each will give about twenty-five tons per loader a day. MEMBER.-How much timber do you use? GLENN B. SOUTHWARD.-A little more than will be used in room-and-pillar work, but not a great deal more. We have not attempted to recover much of our timber. MEMBER.-IS the mine union or non-union? GLENN B. SOUTHWARD.-Non-union. HOWARD N. EAVENSON, Pittsburgh, Pa.-I went .through that mine some weeks ago, and think that the author has been very conservative in his statements about the amount of loadings, etc. EDWARD B. RAIGUEL, Huntington, W. Va. (written discussion).¬Page 7 shows 60 men employed in day and night shifts, inside the mine, producing 750 tons per day. Let us reduce these figures to a man-hour basis, for comparison with Mr. Eavenson's figures on West Virginia mines, as follows:

Jan 6, 1924

By Stuart S. Forbes

Changes and additions made to the Canadian Copper Refiners Ltd. electrolytic refinery between 1949 and 1955 are reviewed. The effect of high current density on current efficiency and section work is discussed. OPERATING and physical changes which have been made to the electrolytic tank house of Canadian Copper Refiners Ltd. suggest a review of present conditions. Previous papers1 a have described the general arrangement. Since then, expansion, closer anode spacing, and higher current densities have increased annual cathode capacity from 112,000 to 182,000 tons. A recent extension to the tank house, begun in the spring of 1954 and completed in August 1955, was undertaken to handle the monthly production of about 3,000 tons of anodes from Gasp6 Copper Mines. The anticipation of these additional receipts and large stocks of unrefined copper caused by the increase in custom smelting at Noranda made it necessary to increase production without immediately available additional cell capacity. Accordingly, from December 1954 through March 1955, the tank house was operated successfully at a current density of 24.0 amp per sq ft. Again, as of September 1955, one of the two tank house circuits is being operated at this high density. Although other refineries may operate at current densities higher than 24 amp per sq ft, none is doing so with anodes which contain silver and gold content as high as those being refined at Canadian Copper Refiners Ltd. General Arrangement The original building consisted of two parallel bays, each 660 ft long and 60 ft wide, with a 24 ft pump bay extending along the west side of the building. A previous expansion, completed in 1939, was to the west of the original building and consisted of two 60 ft parallel bays 240 ft long. The length of these two bays was extended in 1954 to 540 ft, adding one stripper and 12 commercial sections to No. 2 electrical circuit. Space is still available for an additional six commercial sections and one stripper section. Construction on these seven sections started in September 1955, and will be completed early in 1956. The tank house capacity will then be 206,000 tons of cathodes per year. In the two tank houses there is a total of 900 cells distributed as follows—commercial, 468; stripper, 36; total, 504 in the No. 1 tank house (No. 1 circuit): commercial, 360; stripper, 36; total, 396 in the No. 2 tank house (No. 2 circuit). Section arrangement consists of nine cells to a tier and two tiers or 18 cells to a section. Anodes, weighing 620 lb each, are cast with a Baltimore groove and are refined by the multiple system. Solution enters each cell through a bottom inlet at one end and overflows at the top of the opposite end. Rate of solution flow through the cells is controlled by valves at each section to 4.5 gpm. Electrical power to the tank house is now provided by nine 675 kw motor generator sets. Each set consists of a 135-12 v 5000 amp dc generator, driven by a 980 hp 2300 v synchronous motor. When No. 1 circuit is operated at 22,000 amp, five sets, at 4400 amp each, are connected in parallel. As the maximum allowable current on No. 2 electrical circuit has recently been set at 18,000 amp, only four sets are connected in parallel on No. 2 circuit. A tenth set, now being installed, will be reserved as a spare, for use in either circuit as required. Recent Changes In 1949, the annual capacity of the tank house was increased from 112,000 to 132,000 tons by closing the

Jan 1, 1957

By W. E. Remmers

The defect in wire known as "cuppiness" has appeared and disappeared from time to time but the exact cause of its appearance or disappearance has not heretofore been known definitely. This defect is not limited to one particular metal or alloy but seems to be found at various times in all of the materials that are drawn into wire. Fig. 1 represents cuppy wire made from an aluminum alloy and Fig. 2 illustrates copper wire that became cuppy in drawing without intermediate annealing. Differences of opinion are current among the manufacturers of wire and in the literature (see bibliography at end of paper), some believing that the source of the trouble lies in segregation in the wire rod, oxides, sulfides, slag, etc.; others that the trouble is created by an unevenness of stress distribution across the section of the wire, usually thought of as being a function of die shape. All of the published work is of a qualitative rather than a quantitative nature. With this in mind, it was deemed advisable to make a study of the shape of the wire-drawing dies, as well as the oxygen content of the copper to be drawn. Experimental After several methods were tried, it was found that by studying the contour of the butt-end of the rod after drawing a measure of the "working" across the section of the wire could be made. The butt-end of the annealed rod was not sheared but was sawed off. The end was then smoothed with a fine file so that the plane of filing was perpendicular to the drawing axis. It is to be noted that this method is not an absolute measure of the distribution of cold working but is a very good indicative means of studying comparative values. The method of examining a tension break in wire was found to be the most sensitive in detecting cuppiness. Other methods, such as microscopic examination of longitudinal sections, X-ray radiographic studies, etching away of outer layers with nitric acid, and fracture by bending, can all be used to identify cuppy wire but the tension break will give the fracture characteristic of cuppiness before any of the other methods can

Jan 1, 1930

By J. P. Nielsen, H. Margolin, E. Ence

The Ti-Ni phase diagram has been investigated up to 68 pct Ni with iodide titanium base alloys by metallographic, X-ray, and melting point methods, and from 68 to 90 pct Ni by examination of as-cast structures of sponge titanium base alloys. NVESTIGATION of the nickel-rich portion of the I Ti-Ni phase diagram was first reported by Vogel and Wallbaum in 1938.' This work was subsequently extended to lower nickel contents by Wallbaum' who indicated the possibility of a eutectic reaction for nickel contents below 38 pct. Long et al.3 studied the titanium-rich portion of the phase diagram and found eutectic and eutectoid reactions below 38 pct Ni. However, the temperature of the eutectic indicated by Long et al. was considerably lower than that suggested by Wallbaum. Long and his coworkers synthesized their alloys by powder metallurgical techniques and encountered oxygen and/or nitrogen contamination. Thus the diagram which was obtained did not represent binary alloying conditions. However from these results the features of the binary diagram were predicted. At Battelle Memorial Institute4 the Ti-Ni diagram was investigated up to approximately 11.5 pct Ni with sponge titanium alloys. The range of temperatures used was not sufficient to define the eutectoid temperature or composition. The data of Wallbaum2 and Long et al.8 were of particular interest for the present study, and although the work was originally concerned with the region below 40 pct Ni, the investigation was extended to higher nickel contents in an attempt to resolve the differences between these workers. Experimental Procedure Preliminary work on the Ti-Ni system was carried out with duPont Process A sponge titanium alloys to reduce the amount of subsequent work to be done with iodide titanium base alloys. The sponge titanium used contained 99.71 to 99.77 pct Ti, 0.1 pct Fe and 0.005 to 0.009 pct Ni. The iodide titanium obtained from the New Jersey Zinc Co. contained 99.9 to 99.95 pct Ti. Nickel used with sponge titanium was 98.9 pct pure. The high-purity nickel alloyed with iodide titanium was cobalt-free with approximately 0.05 pct C and was obtained through the courtesy of the International Nickel Co. The 15 g sponge titanium charges for melting were prepared by compacting in a die or by placing the weighed portions of nickel and titanium directly into the furnace. Iodide titanium charges were made by drilling holes in the as-received rod and inserting the nickel or by wrapping the nickel in sheet. Sponge titanium alloys containing from 0.2 to 90 pct Ni and iodide titanium alloys containing 0.2 to 68 pct Ni were prepared by these methods. In addition to these alloys several 1/2 1b sponge titanium alloys were supplied by the Allegheny Ludlum Co. The charges were melted in an arc furnace under an argon atmosphere. The procedures used were similar to those reported in the literature5,' and the furnace has been described.' Except for iodide titanium alloys with 40 to 68 pct Ni (see section on copper contamination), each alloy was melted for 1 min, then either turned over or broken before re-melting for an additional minute. Currents of 200 to 400 amp were used depending on the melting point of the alloy. Prior to heat treatment, alloys containing less than 14.5 pct Ni were hot-forged at 750°C. With the exception of alloys in the homogeneity range of the compound TiNi, alloys of higher nickel contents could not be hot-forged. Heat treatment of iodide titanium base alloys was carried out in argon-filled quartz capsules which were broken under water at the conclusion of heat treatment to quench the specimens. Temperatures were controlled to ±5oC and annealing times up to 48 hr were used. For melting point determination, specimens were placed in carbon crucibles which were in turn en-capsuled in argon-filled quartz capsules. The start of melting was determined by rounding of corners and by metallographic examination. Complete melting was considered to have occurred at that temperature at which the specimen assumed the shape of the crucible. Specimens were prepared for metallographic examination by mechanical polishing or by an electrolytic procedure." For alloys containing up to 80 pct Ni Remington A etch7 50 pct glycerine, 25 pct HNO,, 25 8 HF) was used. For higher nickel alloys aqua regia and Carapella's etch (5 g FeCl,, 2 ml HNO,, and 99 ml methyl alcohol) were employed. Specimens to be exposed for powder patterns were prepared by filing, by breaking specimens in a

Jan 1, 1954

By E. A. Gulbransen, J. W. Hickman

ONE of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film A comprehensive program has been undertaken to study these phenomena This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C Before the introduction of the electron diffraction technique, it «as necessary to use either direct chemical analyses or X-ray diffraction analyses to determine the nature of the oxide film formed on the metal or alloy Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry In special cases the information obtained may be identical, but in general both view-points are necessary Much of, the early work was carried out on the oxidation of bulk samples where thick films were obtained The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses Although much useful information has been obtained in this manner, little could be learned about the character of the protective oxides during the period when the films were actually protective Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective LITERATURE The oxidation of iron has been extensively investigated by X-ray and electron diffraction Jackson and Quarrell1 found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe304, between 515° and 900°C the stable film was FeO Above the upper change point of iron the oxide was found to be Fe304 prom 400° to 515°C , FeO, Fe304 or a mixture of the two oxides was found Recrystallization of the air-formed film below 400° and above 900°C led to the formation of Fe304 In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described

Jan 1, 1946

By S. E. Bronisz, Dana L. Douglass

a Uranium was deformed by cold rolling, and the effects of this plustic deformation on the microstruc-ture of the metal were observed by the technique of transmission elecbon microscopy. The recrystalli-zation of selected cold-wmked samples was also studied by this method. The samples were prepared for examination by electrolytic thinning in a standard metallographic electrolyte which has not been previously reported as being used in producing thin foils of uranium. The microstructural changes observed in the a uranium were generally similar to those seen by optical microscopy. The changes in the microstructure of a uranium following cold work and recrystallization treatments have been the subjects of several studies employing optical and X-ray techniques.12-19 These studies indicated that twinning was the redominant mode of deformation at room temperature20 and that the regions of high energy associated with the deformation twins were preferred sites for the initiation of recrystallization.15,18, Recently several workers have prepared thin foils of uranium suitable for examination by transmission electron microscopy.'-lo The foils thus prepared have been used to study fission fragment damage; a particular dislocation reaction,' and gas precipitation." At this laboratory the microstructural changes occurring during the cold working and recrystallizing of a uranium samples have been studied by using transmission electron-microscopy techniques. The foils used in this work were electrolytically thinned in a polishing bath not reported previously in the literature as being used for this purpose. EXPERIMENTAL PROCEDURE The uranium used in this investigation was depleted a uranium sheet 4 mils thick. The results of a spectrochemical analysis of this material are shown in Table I. The as-received uranium was cut into strips, 1 in. wide by 5 in. long, and annealed in vacuo at 600°C for 2-1/2 hr. The resulting microstructure consisted of relatively uniform, equiaxed grains having diameters of 10 to 50 p. Cold Working. The cold-worked samples were prepared by rolling several of the annealed uranium strips to various thicknesses. The strips were reduced 3.5 ± 0.5, 6.0 ± 0.6, 10.0 ± 0.5, 19.5 ± 1.0, and 28.5 ± 2.0 pct in thickness. It was not possible to achieve these reductions with a single pass through the rolling mill, so the strips were turned end for end during the rolling procedure. The cold-rolled strips were stored in dry ice until samples from them could be thinned and examined (within 24 hr after rolling). Annealing. The samples used in studying the re-crystallization behavior of a uranium were obtained by annealing sections of the strips which had been reduced 10.0 and 28.5 pct. These samples were sealed in evacuated Pyrex capsules and were annealed in a tube furnace at temperatures from 200" to 600°C and for times from 1/2 to 2 hr, see Table l. Thinning: The samples from the rolling and heat treatments were prepared for examination in the electron microscope by electropolishing in a bath composed of 25 g chromic acid, 133 ml glacial acetic acid, and 25 ml water. This electrolyte has been used and recommended for preparing specimens for optical metallography It was necessary to mask the edges of the sample with a stop-off paint in order to prevent preferential attack in these areas. The paint used was made by dissolving polystyrene in benzene. The electrolytic cell consisted of a cylindrical stainless-steel cathode placed in a beaker containing the electrolyte, with the sample as the anode positioned at the cell axis. The temperature of the electrolyte was held below 15°C by cooling with liquid

Jan 1, 1963

R. L. Fleischer (Department of Metallurgy, Massachusetts Institute of Technology)— The authors have presented valuable observations of oehavior of aluminum at intermediate and high temperatures. I should like to consider their interpretation of the appearance of cross slip plane traces in sample B-3 as partly due to "bending of the crystal due to grip constraint." Because bending moments might be set

Jan 1, 1960

By N. J. Grant, E. Gregory

The creep rupture properties of wrought aluminum powder products made from five grades of sintered aluminum powder were investigated at temperatures from 400° to 900°F for rupture times up to 1000 hr. The effect of stress concentrations on materials of this type was investigated by means of notched creep rupture tests. A tentative correlation was obtained between the creep rupture properties and the structure as revealed by electron micrographs. SEVERAL papers have been published recently concerning the production and properties of wrought aluminum powder products and their possible high temperature applications. Most of the published work in this field has come from abroad, notably Switzerland, and articles by Irmann and his colleagues were summarized in English recently.'.' Most of the papers published by Dr. Irmann are principally concerned with the retention of properties (by a product which is produced from extremely fine flake powder and is subsequently hot extruded) after heating to high temperature for prolonged times. The powder may be in atomized or flake form, and during hot working the applied pressure is reported to plastically deform the aluminum powder, thus breaking the oxide skin and welding the particles together. Irmann attributes the remarkable properties to the dispersion of oxide inclusions. Specifically, the product described by Irmann is one labeled SAP (Sintered Aluminum Powder) in which the initial flake powder is so fine that at least 50 pct of the flakes have one dimension of 2 microns or less. The composition of the starting aluminum shows in percent, Fe, 0.18; Si, 0.19; Zn, 0.06; Ti, 0.03; Cu, Mn, Mg, all nil; balance Al, approximately 99.5 pct. Aluminum is not the only material that has been found to have increased resistance to deformation at elevated temperatures when produced by powder metallurgy. It has been reported by Middleton, Pf eil, and Rhodes- hat platinum has a higher recrys-tallization temperature when produced by powder metallurgy and exhibits peculiar properties, many of which are similar to those of the aluminum powder products. Difficulties were encountered in explaining the reason for the strengthening in the case of platinum since the existence of the oxide is doubtful. The authors attributed the special properties to "a small amount of suitably dispersed porosity." This theory was supported by von -~eer-leder4 in the discussion to the paper, and the similarity between this method of hardening and that suggested by Rohner in his theory of age hardening was pointed out. R. de Fleury5 attempted to explain some of the properties in terms of the modulus of elasticity and elastic limit of alumina and aluminum while von Zeerleder examined the relationship between the yield strength and the reciprocal of the powder particle size. Boenisch and WiderholtQ dealt mainly with the corrosion resistance of the powder aluminum material and compared it with other aluminum alloys. The diffusion rates of other metals in SAP and pure aluminum have been compared by Seith and Lop-mann.' They showed that the alloying metals diffuse particularly quickly in SAP possibly due to the very fine grain size. The properties of the Alcoa products were given by Lyle.' The creep rupture properties of SAP and two of the Alcoa experimental powder products were compared by Gregory and Grant hnd it was shown that these products are vastly stronger at 900°F than are the best cast and wrought alloys at 600°F. Since the publication of these data, the authors have investigated two further aluminum powder products and it is the object of this paper to show how the high temperature creep rupture properties of the five materials vary with oxide content and with the structure as revealed by electron microscopy. Materials One of the five products, SAP, a sintered aluminum product, was supplied by the Societe Anonyme pourl Industrie de l,Aluminium, Neuhausen a/RHF, Switzerland, through Dr. R. Irmann, while the others, M276, M257, M293, and M255 were supplied by the Aluminum Company of America as experimental powder metallurgical products. M255- and M293 were made from coarse and fine atomized powders, respectively. The other materials were made from flake powders with significant differences in oxide content, the details of the type of powders used in the manufacture of these materials

Jan 1, 1955

By W. W. Stephens, W. J. Kroll, H. P. Holmes

THE only two methods for producing commercial quantities of malleable zirconium, up to now, have been using magnesium reduction of the anhydrous chloride under a neutral gas, and using purification of raw zirconium by the iodide dissociation method on a hot filament. The purity of the metal obtained by the latter process is about the same as that resulting from the chloride reduction, with the exception of the oxygen content, which may be about 0.05 pct lower in the iodide metal. Even traces of oxygen have a strong hardening effect on zirconium. Since, in the iodide process, the impurities, Si, Al, Fe, Ni, and Mg in the raw zirconium used, are carried over, it would appear uneconomical to use this method of refining solely to eliminate the traces of oxygen, unless very soft metal is desired. One important step to improve the iodide method, namely, dissociating pure iodide made from carbide and recycling the iodine, which would change this refining process into a method for extracting zirconium from the ore, has not yet been made. The Bureau of Mines, by using the chloride reduction, wanted to produce quantities of a reasonably pure and malleable metal at low cost for large-scale industrial use. This aim has been achieved, and a pilot plant permitting production of 600 lb of malleable zirconium per week will be described (fig. 1). Briefly, the Bureau of Mines process consists of reducing purified gaseous anhydrous zirconium chloride with fused magnesium under a noble-gas atmosphere. The reaction product, magnesium chloride, and any excess magnesium metal present are removed from the sponge zirconium in the next step by fusion and evaporation in a good vacuum at about 925°C. In this process, care is taken to keep air out of contact with the hot metal, which otherwise would contaminate the product with oxygen and nitrogen. Both these impurities embrittle zirconium even when present in an amount as low as 0.1 pct. A number of previous reports1-3 describe the method and the various improvements that finally led to a workable process. The major steps made were the production of large quantities of carbide, which is the raw material for producing the chloride, its chlorination with reasonable efficiencies, and the elimination of iron trichloride contained in the raw chloride, as well as that of the zirconium oxide which is always present in this product. The physical nature of the anhydrous chloride, which sublimes at 331°C at atmospheric pressure and melts at 420°C under a pressure of 25 atm, made it necessary to provide a special safety device on the purification and reduction vessels in the form of a lead-alloy seal, permitting escape of excess gases if pressure tended to build up. The main difficulties encountered in the reduction and in the following step, salt separation in a vacuum at elevated temperature, were caused by the material from which the reaction pot was constructed—iron. This metal reacts with zirconium at about 940°C with formation of a eutectic. The last step, salt separation by evaporation of the magnesium and magnesium chloride in a vacuum, is quite unconventional and has not been used before on such a scale. It is only due to the improved construction of high-vacuum pumps, especially oil-diffusion pumps, that such a method could be used. The various steps of the Bureau of Mines process, as described in the general outline above, may be summarized as follows: (1) production of the carbide, (2) chlorination of the carbide, (3) purification of the raw chloride, (4) reduction of the pure chloride with fused magnesium, (5) separation of excess magnesium and magnesium chloride in vacuum at elevated temperature, and (6) melting of the sponge obtained. Production of Carbide The arc furnace, described in a previous report,' was improved both to reduce the graphite consumption caused by the burning of the bottom plates and to concentrate the heat in order to obtain better power efficiency. This was achieved by providing the bottom with graphite plates entirely embedded in refractory bricks, the contact with the current being made with three water-cooled copper plugs. Figs. 2 and 3 show the arrangement. The crucible, made

Jan 1, 1951

By Rudolph G. Wuerker

MUCH descriptive matter[ ] has appeared on the subject of suspension roof supports, or roof bolting, as it is more commonly called. The wide- spread introduction of roof bolting into coal mines and metal mines is truly phenomenal. Mine operators were quick to recognize the advantages of supporting wide openings without hindrance to machine maneuverability and ventilation.

Jan 6, 1953

By J. L. Huitt, B. B. McGlothlin, J. J. Day

Laboratory tests were made with pure minerals and actual reservoir rock samples to study the effects of hydrothermal (steam m hot water) treatments on reservoir rock properties. These tests showed that hydro-thermal treatment of many reservoir rocks can result in significant rock softening. The softening was attributed primarily to the partial destruction of dolomite and kaolinite and the synthesis of montmorillonite in the presence of excess silica. In many cases, the softening was great enough to cause considerable healing of propped fractures; therefore, a serious reduction in welt productivity could result. In other tests it was found that the addition of ammonia to a hydrothermal treating fluid in a concentration as low as 0.013 Ib/lb of water not only could prevent rock softening but could cause rock hardening. The results of X-ray diflraction analyses of rock samples showed that when ammonia was added to the treating fluid, ammonium-mica and analcite were formed instead of montmorillonite. No significant permeability damage was observed in the sandstones that were subjected to the ammonia-hydro-thermal environment; in some sandstones, permeabifity improvements resulted. INTRODUCTION As the use of steam or hot water becomes more prevalent in well stimulation methods. the need for information on the effects of such treatments on reservoir rock properties becomes increasingly apparent. Several works have been published on high-temperature changes in rock properties,',' but these are more applicable to in situ combustion operations than to steam or hot water injection processes. The mineralogical literature contains many publications which report on the changes occurring with various pure minerals in hydrothermal systems. A review of this literature denotes the ease with which entirely new, crystalline mineral phases can be synthesized from other minerals in hydrothermal environments at temperatures, pressures and residence times typical of those encountered in oilfield thermal recovery or stimulation processes. Discussions of many of these experiments are given by Deer et al. Grim,' Roy et al., Zen\ and Hawkins.' One of the most significant of these pure mineral studies is the hydrothermal synthesis work of Levinson and Vian" in which montmorillonite was synthesized from naturally occurring minerals; i.e., kaolinite, quartz and carbonate minerals (particularly dolomite). These reactions occurred at 575F in only 2 days and at 300F in 5 days. These results may be applicable to petroleum reservoir rocks since the minerals studied were those which are commonly found in sandstones. Furthermore, the environmental conditions imposed in the studies were very similar to those involved in thermal stimulation of petroleum reservoirs, e.g., steam or hot water injection. Other studies have suggested that weak rocks could be hardened by "electrochemical induration", a process in which an electric current is applied to a clay-containing rock body. These tests can be regarded as hydrothermal treatments since they were conducted in some instances with aqueous solutions and since clay temperatures during the electrical treatment reached a maximum of about 100C. Although a number of studies of the reaction of pure minerals have been reported, very little has been published on the reactions of petroleum rock-hydrothermal systems. No work has been reported on preventing the more detrimental rock changes in rock softening which might occur during the injection of steam or hot water into reservoirs. The studies described in this paper were conducted to provide such information. EXPERIMENTAL APPROACH The laboratory tests included studies of the effect of hydrothermal treatment on core samples from several different reservoirs. The hydrothermal treatments (simulated steam treatments) were conducted with distilled water at 575F, for the most part, for periods of 2 to 6 days. This temperature level was selected because it represented that temperature which would probably prevail in several cases under consideration for steam injection projects. The core samples, as well as the pure mineral samples, were contained in high-pressure stainless steel, autoclave-type pressure vessels. The effects of the hydrothermal treatments were evaluated by measuring the penetrometer hardness, formation rock embedment strength and permeabilities of the core samples before and after the treatments (Fig. 1)'" In addition, the mineralogical changes in the specimens were studied by X-ray diffraction. Concomitant with the core sample studies, the mineralogical changes were studied in greater detail by conducting hydrothermal synthesis experiments with pure minerals at similar temperature levels and residence times. For the most part, samples of finely-crushed pure dolomite.