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By H. M. Otte, A. G. Crocker

SLIP, twinning, stacking faults, and precipitates on well-defined planes in a crystal produce traces that are visible on either a polished or an etched surface. The purpose of this note is to establish the usefulness and limitations of the information obtained from such traces when determining the orientation of single crystals or grains in a polycrystal. Attention will be confined specifically to traces produced by octahedral planes in cubic crystals, though most of the remarks can be taken as more generally valid. The problem of determining the crystal orientation is completely solved in principle' and in particular for the special case under consideration.1'2 Tables are available3 in which the orientations can simply be looked up when given the two or three angles between the traces. Thus a quick and simple method is available for obtaining the orientation of a crystal from surface traces. In this note two examples will be given from recently published papers and will show the use of the method with the aid of the Tables, as well as some of the precautions that should be taken in the procedure. As part of an analysis of X-ray Kossel lines, Peters and Ogilvie 4 determined from them the crystallographic orientation of the specimen. They chose a Cu-5.10 wt pct Si alloy that had been partly transformed from the a (fee) phase to the k (hcp) phase. The latter formed as very straight platelets along the octahedral planes of the a phase, and a photograph (Fig. 7 of Ref. 4) was reproduced in the paper4 of the region for which the orientation had been determined from the Kossel lines. Apart from a very small area (about 0.15 mm diam) near the top center of the photograph, the region shown was clearly all of one orientation. Traces in four different directions were readily identified. Starting with the smallest angle and proceeding counterclockwise, the angles between the traces were measured to be 27° 43', 55° 16', 64 3 43 1, and32"26'. These add up to 1802 08 1, indicating a cumulative error of 8'. The correct values should, of course, be taken from the original glass plates, or at least from prints on distortion-free paper, so the precision of the quoted values is actually greater than their accuracy. The solutions can be looked up in the Tables3 in four ways, depending on how the angles are paired, tion for the minutes of arc is required and the solution obtained will be identical for all the four pairs if the values of the angles are not in error. In a practical situation, such as this one, there are several sources of error, so that the four solutions obtained will all be slightly different. An arithmetic average of the four solutions is mathematically incorrect, but may, in special cases, give an answer close to the correct one. A rigorous procedure for refining the orientation has been described by Mackenzie;5 he gives a least-squares method that can be applied, if necessary, to this type of problem. The orientation thus determined can be compared with the one from the Kosel lines and discrepancies larger than the experimental error assigned to nonor thogonality of the X-ray or electron beam to the specimen. Here the example will only be used to illustrate the general procedure for making a very rapid rough check. From measurements on the stereographic projection, Fig. 9 of the paper,4 we can determine that the surface normal is approximately (0.434, 0.704, 0.562). From the Tables3 we find, using 28°, 55" as a good approximation to the first pair (27°43', 55°16'), that the surface normal is (0.453, 0.678, 0.579).* These two values are within 2 deg of each

Jan 1, 1967

By James Hance

INTRODUCTION SEVERAL years ago the writer was connected with the Mint and Assay Service of the Federal Government as Assistant Assayer at the-Salt Lake Assay Office. At that time cyanide bars formed approximately half of the bullion purchased by that office. Disagreement in valuation between the producer and the office was not infrequent and to a lesser extent between the Assay Office and the Mint, this latter issue being soon obviated, however, by adopting uniform methods of sampling the bars. A nice problem seemed to offer itself for research and the writer began a series of experiments which were soon terminated, however, by his going into other work, and which he regrets have not since been completed. The results attained may suggest lines of approach to this problem and are, therefore, offered in this article. Frederick P. Dewey, Assayer of the Mint Service, U. S. Treasury, has had abundant opportunity to study this phase of metallurgy, and has published several articles relative thereto.1 In the last article cited Dewey quotes analyses of cyanide bullion similar in content to that with which the writer worked, and which show some of the variations met with. In the discussion of these papers,2 comparison has been made in terms of copper bullion, but to the writer this seems of questionable value. Copper bullion may resemble silver bullion, but its similarity to, gold bullion with little or no silver content is another thing. The freezing-point diagram of Roozeboom, reproduced on page 881 of the discussion cited, is for the gold-silver series as stated. The original problem under discussion, however, is not this alloy but gold with base metals other than copper. As for the statement that the corners are the worst places or

Jan 2, 1916

With a total value to date of well over $200,000.000.00 for its ore production, the Tintic mining district, which is about 100 miles southwest of Salt Lake City, ranks as one of the three main ore producing areas of Utah. In it are located the biggest silver mines of the country, silver having been the chief metal produced in the camp since its start. Tintic's silver production to date has a total value of over $1 00,000,000, approximately half of the value of the camp's ore production, the balance being roughly divided among lead, gold and copper. Discovery of the camp was made in the late sixties. Lack of transportation and ore reduction facilities delayed extensive development of the area for nearly a decade. In recent years Tintic's ore production has ranged from 350,000 to 400,000 tons annually. In 1924 the camp produced one-eighth of the silver produced in the nation with an output of 7,729,700 ounces. Its lead production was 77,765,000 pounds and its gold production 26,285 ounces.

Jan 1, 1925

By L. K. Jetter, J. C. Ogle, C. L. McHargue

The preferred orientation developed in extruded aluminum rods has been studied as a function of extrusion temperature, extrusion speed, and position in the rod. Duplex <111> - <001> textures were developed for slow extrusion speeds at temperatures of 75° to 850° F and for fast extrusion speeds at temperatures of 75° to 450°F. The <001> texture component was shown to be primarily due to re crystallization occurring during fabrication. At fast speeds and billet temperatures of 650° to 850°F, complete recrystallization occurred and <115>or<118> textures were found. The nature of the structure has proved to be an important variable in the production and use of extruded products. Data on the flow of aluminum and aluminum alloys summarized by Smith,&apos; Hardy,&apos; and Locke3 show that the extruded product may possess a deformed, a partially recrystallized, or a completely recrystallized structure, and there may be important variations in the structure from surface to center and from front end to back end of an extrusion. This inhomogeneity in grain structure and preferred orientation affects both the mechanical properties of the extruded section and its response to subsequent heat treatment. Among the fabrication variables causing these differences are temperature, extrusion ratio, and extrusion speed. Preferred orientation which develops during the extrusion of rods is of the fiber-type and, in general, has been assumed to be similar to that developed in rods or wires fabricated by drawing through dies, rolling, or swaging.4 Because of the nature of the flow of metal being extruded, this assumption may be valid for material near the center of the rod but probably is not valid for the outer layers. In most face-centered-cubic metals a duplex fiber texture has commonly been reported in which the grains have either <Ill> or <001> directions parallel to the longitudinal axis. Sachs and fichiebold5 reported cold-drawn aluminum (99.6 pct pure) to have a single <Ill> fiber texture, and this observation was confirmed by Schmid and Wassermann.6 Hibbard, on the other hand, observed a minor <001> and a major <111> texture in 99.994 pct A1 cold drawn to 98 pct reduction in diam.7 He concluded that the <001> component resulted from a small amount of room-temperature recrystallization. Dayal8 concluded that the <001> component was an intermediate component which disappeared at high reductions in 99.5 pct pure Al. Kostron and schippers9 found duplex <111> — <001> textures in extruded 99.5 pct Al, as did Gow and cahnl0 and GOW11 for extruded rods of commercial and superpure aluminum. Similar duplex fiber textures have been reported for aluminum alloys by Kostron,= Unckel,13 and Van Horn.14 The present paper is concerned with the variation in texture with fabricating conditions and with the nature of the texture components in extruded aluminum rod (99.99 pct pure). EXPERIMENTAL PROCEDURE Ingots were chill-cast in cast-iron molds and machined to 3-in. diam by 6-in. long extrusion billets. These billets were upset to 3.125 in. diam and extruded through a flat-face 0.690-in. diam die. Quenching of the rods was accomplished by a water spray at the die face. The combinations of fabricat-

Jan 1, 1960

By Gordon E. Frantti

Under the auspices of the Geophysical Committee of Michigan College of Mining and Technology, an investigation was made in Michigan&apos;s Upper Peninsula to obtain geophysical data related to the regional subsurface geology in the area covered by Paleozoic sediments. The area surveyed includes that portion of the Upper Peninsula which lies between R18W to R26W and T41N and T49N, covering approximately 1300 square miles. On the index map, Fig. 1, it is represented by the cross-hatched zone west of Munising. Four of the five sites of detailed investigation are indicated by the letters A, B, C, and D. A detailed gravity and magnetic survey had previously been conducted by J. G. Wilson near Perkins, 8 miles north of Rapid River, on a local anomalous area. Results of his work, which showed a large positive magnetic anomaly associated with a gravity anomaly, aroused interest in the possible economic significance of the formations underlying the Paleozoic sediments in this part of the Upper Peninsula.

Jan 1, 1956

THE shipments of high-grade manganese ore, con-taining 35 per cent or more of manganese, from the mines in the United States in 1926 were slightly less than half as large as similar shipments in 1925, accord-ing to the United States Bureau of Mines, Department of Commerce. The shipments in 1926 by 45 producers amounted to 46,258 long tons as compared with 98,324 long tons by 42 producers in 1925. This decrease was due to the falling off of the shipments from Montana. The domestic production of metallurgical ore in 1926 was 26,530 tons; that of chemical ore, 19,728 tons. Montana was the largest shipper with 5713 tons of metallurgical ore and 17,904 tons of chemical ore. The largest individual shipper of metallurgical ore was the Crescent Mine in the Olympic Mountain Region, Clallam Co., Washington, from which the shipments for the year were 3162 tons. The mine was operated by lessees and reverted to the owners in July, and thereafter to the close of the year no .ore was shipped.

Jan 6, 1927

By Orlando Romig

PART I-PREPARATION OP METALLIC SINGLE CRYSTALS WITH ESPECIAL REFERENCE TO SINGLE CRYSTALS OP ZINC? As metals and alloys are composed, of, an aggregate of allotriomorphic crystals or grains, each possessing an individual orientation, the physical characteristics of a metal or an alloy are closely related to the properties of the individual crystals. The preparation and study of single metallic crystals are, therefore, matters of considerable importance. The advent of the X-ray spectrograph as a valuable metallurgical tool has magnified the importance of this subject, because the interpretation of some X-ray spectrographs is difficult unless single crystals are used in these studies. PREVIOUS WORK The first paper, as far as the writer knows, on the behavior or preparation of single crystals of metals is by Baker.1 He describes the behavior of extruded wires of sodium and potassium. These wires, when pulled in tension, instead of I showing the usual conical fracture common to most metals, had a chisel-shaped fracture when they were broken. I and II, Fig. 1, have a similar fracture. Baker checked his results by preparing single crystal wires from molten sodium and potassium and observing their properties. He prepared the wires by filling glass tubes, under oil, with the molten metal. The surfaces of the strained wires showed slip bands of remarkable clearness of which photographs are shown in his paper. He concluded that these wires were single crystals and "that the portions of the metal brought into play are cubes. Such cubes, when placed so that a plane through &apos;two opposite edges was parallel to the axis of the wire, would allow of lateral contraction by faces gliding over one another in one direction only and not in the direction at right angles."

Jan 1, 1927

By AIME AIME

AT FOUR O&apos;CLOCK members gathered in the auditorium for the annual business meeting of the Institute which, according to its charter, must be held on the third Tuesday of February each year. President Turner presided and after the usual formal action on minutes announced that he would create a precedent by transferring the President&apos;s annual address (which by tradition has always been delivered at the banquet on Wednesday evening) to the business meeting, and, furthermore, would only present a brief abstract of it. Since it appears in full on pages 127-131 of this issue it can be followed with the careful attention its thoughtful analysis of current conditions deserves.

Jan 1, 1933

By Keats, J. L.

IN THE literature on the elimination of metalloids in basic open-hearth practice, there are a great many heats recorded in which excellent data on changes in slag and metal composition during refining are given, but in almost all of these heats either temperature data or weights and analysis of charge are unrecorded and observations on the physical charac- teristics of the slag are almost always lacking. With these points in mind, a test heat was made in which as complete as data possible on all the factors that affect the elimination of metalloids were obtained.

Jan 1, 1957

(Under this heading will be published notes sent to the Secretary of the Institute by members or other persons introduced by members) Member, Graduate Colorado School of Mines. Four years&apos; experience in West and Northwest. Two years with American Smelting and Refining Co. Wishes to join field party on geological work, mining or areal, where opportunity will be given to be of direct assistance to chief of party in solution of field problems. Age, 26. Unmarried. At liberty June 1. No. 342. Member, technical graduate, aged 30, with&apos; 7 years&apos; experience in concentrating and mining, desires a position of authority with reliable company. At present employed. No. 343. Member. Ambitious, energetic, tactful engineer, college graduate, married, aged 30, desires location with a large coal mining organization. Seven years with present employers -n middle west; has had broad experience in the past eight years on examination, development and construction; successful record in handling men. Position must carry responsible work and a future. Will go anywhere for proper opportunity. Exceptional references as to reliability, character and capacity for work. No. 344.

Jan 3, 1917

By Francis Lucas

EACH year we gather in this auditorium to honor the memory of a . distinguished American metallurgist and educator. I cannot bring to you reminiscences of Prof. Henry Marion Howe as other lecturers have done. It was not my good fortune to enjoy the privilege of studying and ,working under his direction. As I have reflected on the published works of Professor Howe, it has seemed to me that his mind was trained on the nature of metals and on the mechanism which produced known but unexplained effects. He was interested in controlling and regulating the causes so as to produce specific effects, useful in serving mankind. I recall an afternoon in May, 1925, when, at the invitation of Mrs. Howe, I visited his former home, Green Peace at Bedford Hills, N. Y. The purpose of my visit was to receive at the hands of the widow -an engraving of Professor Howe, a reproduction of a painting from life. Mrs. Howe showed me his study. The walls of this large attractive room, brilliantly illuminated by the spring sunshine, were literally covered with the scrolls of honors and of decorations which had been conferred on Professor Howe by governments, academies, universities, societies and. institutions the world over. As we walked about the room, she pointed out the significance of each honor and recited a few details of each occasion. I sensed the pride with which Mrs. Howe, then in the late autumn of her life, told me of her husbands&apos; achievements, of his struggles, of his disappointments and of his successes. There was a surprisingly familiar note in the recital to which I was listening. I have found the same theme running as a disconnected thread through the written accounts of the lives of most men of science. We then went to the drawing room to chat for a few minutes before I said my farewells. As we seated ourselves, Mrs. Howe turned to me and asked: "Mr. Lucas, what of this great microscope of yours? Cannot it be applied to the study of disease? What a great blessing it would be if it could be directed to relieve the suffering of mankind."

Jan 1, 1931

By C. E. Sims, H. M. Banta, S. L. Hoyt

Over the past few years, metallic arc welding has been extended to steels of the hardenable type. As compared with other methods of fabrication, production has been facilitated, service performance frequently has been improved, and the overall results have been so favorable that engineers and production men have placed great emphasis on this application of welding. The metallurgist and welding engineer, however, have been confronted with new problems, since, for one reason, the harder steels are more apt to crack and special precautions must be taken if sound joints are to be procured. Some of the factors that are pertinent to this problem are metallurgical, and it is an object of this contribution to discuss steel manufacture and processing methods and to show how their control assists in reducing the hazard of cracking. By this time, the problem of cracking— specifically underbead cracking, or "hard cracks," or parent-metal cracks-—is well known, and a large amount of work has been published, both here and abroad, dealing with this subject.&apos; The tests described are made under restraint to facilitate cracking and arc so designed that a semiquantitative, or at least a relative, value of the cracking tendency is obtained. As one would expect, it has been reported that the incidence of cracking increases with the carbon and alloy content of the steel. More specifically, the cracking tendency is said to increase with the hardenability of the steel, though it is now recognized that the situation is not so simple. The phenomenon itself, on the other hand, has been but loosely described, and it is in only broad generalizations that this cracking has been related to steel metallurgy. Thus, while it has been abundantly demonstrated that the hardenable aircraft steel, S.A.E. 4130, must tend to crack when are-welded, the problem still remains of why two lots of the same composition and the same hardenability can vary so greatly in cracking tendency, or what it is about the prior metallurgical history that so strongly affects the results. Further, while the efficacy of preheating and postheating in preventing cracking is recognized and utilized in production, the mechanism by which they function seems not to have been described. These points are thought to be significant in the production of steel for fabrication by metallic arc welding and, hence, of interest to mill and process metallurgists and welding engineers. Consequently, it is another object of this paper to discuss the mechanism of parent-metal cracking, including the influence of the condition of the steel and the control of cracking by manipulation of the time-temperature conditions during and after welding. A new method of rating the cracking tendency is also discussed, and the results of the test are related to steel composition and structure or prior history. The work to be described was the outgrowth of work in 1940-41 at Battelle Memorial Institutc on two projects, one

Jan 1, 1945

By AIME AIME

DESTRUCTION of the plants, machines, utilities, tools, materials, and other essentials for peacetime living penalizes not only the owners of the materials destroyed, but the world as a whole. Specifically, the fundamental fallacy of any proposal for the in- discriminate destruction of the German industrial system is that it fails to differentiate between the wartime and the peacetime economy of the Reich. We are for one simple, clear objective-an effective industrial means to keep Germany from starting another war. This objective should not be con- fused, especially before the war is even won, with the appropriate punishment of Germany or with the international arrangements for the long future to be made around the peace table by the representatives of the Allied Nations after victory is achieved. This paper, therefore, does not deal with broad, complex postwar questions of diplomacy and international policy. "Unconditional surrender" implies disarmament of the German armies, the surrender of all arms, munitions, air- planes, and other ordnance material in stock piles or in process. It also should include the elimination of all German war production facilities, such as ordnance plants, munitions plants, and submarine works, and the control of raw materials required by war industries.

Jan 1, 1944

By H. D. Wilde

GREAT emphasis is being placed today on petroleum as a source of chemicals. Such prominence is well merited, for rapid strides have been made in developing processes for the conversion of petroleum into synthetic chemical products, which are now being made on a huge scale. These marvelous accomplishments have resulted in some highly optimistic predictions as to what can be expected in the future. Many of these forecasts are well justified, but some writers, especially those contributing to the Sunday supplements and the popular-cience type of publications, have let their imagination run wild and present a rather distorted picture of the possibilities in this field in the postwar period. Commercial manufacture of synthetic organic chemicals had its beginning in England with the establishment of a plant by Sir William Perkin in 1857 for the manufacture of "Aniline Purple" or "Mauve." The preceding year he had discovered in the laboratory how this dyestuff could be made from aniline, one of the many derivatives of coal tar, and he soon made commercial application of his discovery. Influenced largely by his success, organic chemists began research on production of a vast array of synthetic dyestuffs, medicinals, flavors, scents, and explosives. Rapid progress was made and by the turn of the century hundreds of these products were being manufactured. Most of these synthetic chemicals were derived from materials obtained as by-products in the conversion of coal into coke. These by-products are generally referred to as "aromatics" and are obtained by processing coal tar recovered in the coking process, so they are popularly known as "coal-tar chemicals." During the early years of this century, coal-tar chemistry was the wonder of the age, and rightfully so, since the products so made seemed limitless.

Jan 1, 1944

By H. A. Schwartz, A. F. Gorton, H. R. Payne

In a previous paper1 we published what we believed to be a correct stable equilibrium diagram for an iron-carbon alloy containing + 1.20 per cent. silicon. The purpose of the present paper is to record the results of studies concerning the effect of silicon on the location of the eutectoid points of both systems, including also certain incidental observations of general interest. We prepared white cast irons containing roughly 21/2 per cent. carbon, 0.05 per cent. manganese, and 0.03 per cent. each of phosphorus and sulfur, but of accurately known silicon contents which varied from 0.40 to 3.32 per cent. These were completely graphitized, and both A1 points determined, as in our previous work, the specimens being converted from the stable to the metastable condition and vice versa by appropriate heat treatments. Each stable alloy was heated to a few degrees above Arl for 3 to 7 hr., quenched and analyzed for total and graphitic carbon, the difference being the "combined" or, better, agraphitic2 carbon content of the saturated solid solution just above the eutectoid transformation. One specimen was lost through accident, and the 0.40-per cent. silicon material gave an anomalous result ascribed to difficulty in maintaining the stable system in the presence of but little silicon.

Jan 1, 1923

By H. R. Payne, A. F. Gorton, H. A. Schwartz

In a previous paper1 we published what we believed to be a correct stable equilibrium diagram for an iron-carbon alloy containing + 1.20 per cent. silicon. The purpose of the present paper is to record the results of studies concerning the effect of silicon on the location of the eutectoid points of both systems, including also certain incidental observations of general interest. We prepared white cast irons containing roughly 21/2 per cent. carbon, 0.05 per cent. manganese, and 0.03 per cent. each of phosphorus and sulfur, but of accurately known silicon contents which varied from 0.40 to 3.32 per cent. These were completely graphitized, and both A1 points determined, as in our previous work, the specimens being converted from the stable to the metastable condition and vice versa by appropriate heat treatments. Each stable alloy was heated to a few degrees above Arl for 3 to 7 hr., quenched and analyzed for total and graphitic carbon, the difference being the "combined" or, better, agraphitic2 carbon content of the saturated solid solution just above the eutectoid transformation. One specimen was lost through accident, and the 0.40-per cent. silicon material gave an anomalous result ascribed to difficulty in maintaining the stable system in the presence of but little silicon.

Jan 1, 1923

By E. B. Spice

Although much may be learned about the economics of cold weather operations by studying successful mining ventures in southern and central Canada, it is the purpose of this article to extend the study by considering only permafrost areas. Geographically this means most of the country north of the 60th parallel. In this area, at the present time, only five Canadian companies are carrying on routine and successful mining operations on a year-round basis. However, there have been some score of unsuccessful ventures, and a number of properties in the development stage show promise of being producers. Problems of cold weather are worthy of study. It may be pointed out that successful mines in this area face problems of isolation and costly transportation as well as cold weather. To reach valid conclusions, consider the development of a mythical mineral deposit located on the 65th parallel in the heart of the barren lands; problems of isolation and transportation will be ignored.

Jul 1, 1956

By AIME AIME

A THOROUGHLY satisfactory crowd turned out at the fall meeting of the Industrial Minerals Division and took an active part in the entire program. On Thursday afternoon, Sept. 24, a limestone plant was inspected, technical sessions occupying the attention of the visitors all day Friday and Saturday morning. Headquarters were at the Nittany Lion Inn, an attractive hostel on the Penn State campus, at State College, right in the center of Pennsylvania. We are still in the dark, despite inquiries, as to just what breed of lions Nittany lions are. As nearly as we could find out, Nittany is not a Biblical name, as it sounded to us, but a corruption of the name of an Indian princess, or maiden, or maybe just girl that haunted those parts in bygone times and after whom a near-by mountain was named. Penn State athletes are "lions" and there you are. The meeting was supposed to be a joint one with the American Ceramic Society&apos;s Materials and Equipment Division; but it was quite evident that the Institute had a much better publicity agent than the Society, which bothered Ross. Purdy, the aggressive secretary of the ceramic people, no end. However, Secretary Purdy saw to it that everyone present fully understood that the Ceramic Society was present, so that that contingent all but stole the show, its representatives presiding at every meeting. The Pittsburgh Section of the American Ceramic Society was also supposed to be holding its fall meeting there at the same time, but made no trouble at all for anybody, as one of the speakers remarked.

Jan 1, 1936

By R. P. Abendroth

This study is concerned with the kinetics of selective oxidation of chromium in a commercial Fe-Cr-Ni alloy. Selective oxidation of chromium in this alloy, by use of a low oxygen-potential atmosphere, leads to the formation of a compact, protective layer of Cr2O3. This layer serves to protect this alloy from gross scaling when it is subsequently exposed to severe oxidizing conditions at high temperature. The interaction of low oxygen-potential atmospheres close to equilibrium with Fe-Cr and Ni-Cr alloys has been studied by others."&apos; These studies werk concerned with the surface-structure variations under slightly oxidizing conditions. NO detailed study was made of the oxide scale formation kinetics, however. The alloy samples were cut from 0.012-in.-thick sheet, with an apparent surface area of 7.1 sq cm. These sheet samples were abraded through 4/0 metallographic paper, and washed in alcohol and acetone. The analysis of the sheet alloy is (in weight percent): 42 pct Ni, 5.5 pct Cr, 0.09 pct C, 0.18 pct Al, 0.36 pct Si, 0.26 pct Mn, balance Fe. The weight gain vs time data were obtained with a 2-g capacity fused-silica spring—cathetometer system. The spring deflection was optically magnified ten times before being read by the cathetometer. A sensitivity of about 0.01 mg was attainable. The spring was enclosed in a water jacket maintained at 60°C to minimize the effect of temperature changes. The sample was suspended from the spring with a fused-silica hangdown and was positioned in the thermal center of a mullite furnace tube. Sample temperature was read with the aid of a thermocouple placed outside the mullite tube and an inside vs outside temperature calibration. Temperature change during the course of a run was ±0.25°C, with a temperature gradient of less than l.O°C over the length of the sample. Total temperature uncertainty was no more than ±3.0°C. Alignment difficulties between the hangdown and radiation shields in the furnace tube required that the sample be positioned in the furnace when cold, and heated with the furnace until the temperature stabilized at the desired point. This required 5 to 6 hr, and was carried out in Matheson ultrahigh-purity hydrogen. Oxidation was started, after evacuation, by introducing a hydrogen-water vapor mixture, obtained by saturating hydrogen with water vapor at 31.00o ± 0.02oC. Oxidation was continued for 90 min. Gas flow was 300 ml per min during heat up and oxidation. Since only several milligrams of oxide are formed on each sample, chemical analysis of the oxide is difficult. A representative analysis is: 80 pct Cr2O3, 5 pct Fe2O3, 3 pct Al2O3, 4 pct MnO, 7 pct SiO2, 1 pct or less NiO. X-ray diffraction analysis of the oxide as formed on the alloy gives rhombohedra1 Cr2O3, and barely distinguishable amounts of a cubic spinel phase, and possibly AlZOs and SO2. The identification of these latter two compounds is by no means certain. The spinel phase could be based on iron or manganese as these elements are present in significant amounts in the oxide. The results of the kinetic studies using 31°C dew-point hydrogen-water vapor mixtures were found to conform to a parabolic rate law. In many cases the parabolic plot consisted of two intersecting straight lines, defining an early and a late rate for a particular run, and in the other cases the parabolic plot consisted of one straight line for the entire run. The slopes of the various straight lines were determined by the method of least squares. Reproducibility of the data was good enough for multiple runs at the same temperature such that the value given for the rate constant is the average for two or more closely similar values, rather than widely varying values of the rate, where more than one determination is indicated in Table I. The exhibition of only one or of two rate constants during a run can happen at the same temperature. Thus, Table I shows that at 11&apos;74°C a single rate constant was obtained from one sample, while other samples oxidized at the same temperature gave an early and a late rate constant. It should be noted that the single rate constant corresponds very closely with the early rate constant. This is also true at 1153°C. The time at which the late rate started to appear was variable, usually occurring 20 to 40 min after oxidation had started.

Jan 1, 1964

By F. J. Fayers, R. L. Perrine

For many years the problem of increasing ultimate recovery of oil from a reservoir has been a subject of interest to the oil industry. At present, a standard secondary recovery technique is to flood the reservoir with water once natural forces of the system are depleted. The permeability characteristics of the rock, together with interfacial forces which exist between the two fluids and the porous material. allow only part of the oil in the rock formation to be recovered by the water-flooding process. Laboratory experiments have shown that when detergents are added to the flooding water, the flow properties of oil in a porous rock arc improved. This improvement results in greater oil recovery. Even though higher recoveries are obtained using detergents, the extra cost associated with the method may make it economically unsatisfactory. To establish economic feasibility requires experimental laboratory measurement of fluid and rock properties together with a calculational procedure to predict field results. Pilot tests in the field may also be required. This paper presents a mathematical procedure for predicting detergent flood behavior. A number of reasonable simplifying assumptions are made to obtain a tractable system of equations. The resulting method may be regarded as a generalization of Buckley-Lev-crett&apos; theory to solve simultaneously for water saturation and detergent concentration profiles. Consequently this type of calculation can be used in much the same manner as Buckley-Leverett theory is used to evaluate a water flood. The mathematical method employed is the so-called method of characteristics for solving hyperbolic partial differential equations. This application of the method is instructive because several other problems in reservoir analysis may be analyzed in a similar manner. FLUID FLOW EQUATIONS The flow behavior of oil and water without detergent through porous reservoir rock is usually expressed by Darcy&apos;s law and a continuity equation for each phase. If gravitational forces are neglected, vrg = kr (s)µr v p rg.........(1) vrg = kr (s)µr v p rg.........(1) ? pa va = F ?/?t (sd) where v is the volumetric flux, k represents permeability, S is saturation, and P the pressure. Fluid viscosity is denoted by 11, p is the density, 4 is porosity, and I the time. The subscripts w and o refer to water and oil. The capillary forces in the system lead to a difference in pressure between phases. This may be expressed by the relation: Pm -P0 =Pc(S).........(5) The capillary pressure? P,, is determined experimentally as a function of saturation. DETERGENT BALANCE EQUATION Addition of detergent to the water phase affects the flow properties of the system. Capillary pressure and relative permeability become functions of detergent concentration, c, as well as fluid saturation. That is: P--P (S,c) and k,,,.- - -- k,,,. At low oil saturation values, the presence of detergent reduces capillary pressure and reduces the relative permeability ratio. Detergents are surface-active and adsorb on rock surfaces. The quantity adsorbed, a, will depend on the concentration c of detergent solution and may also depend on the saturation; thus, a = a(S,c). In this analysis we have assumed that the detergents used are water soluble but not oil soluble, and their movement is therefore restricted to the water phase. The dispersion of detergent in water is neglected by comparison with transfer by flow within the system. Detergent movement is determined by the water flux and adsorption: ? cv m = -F ?/?t (cs + a) We will assume that the quantity of detergent in solution is too small to significantly change water density or viscosity. When the permeability and capillary pres-