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By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan' investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0'~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther' investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969

By A. M. Turkalo

IT is a well-known fact that martensitic steels show a greater resistance to brittle fracture than do pearlitic and bainitic steels. It was, therefore, thought worthwhile to investigate the mode of brittle fracture with respect to structure by studying the effect of various austenite decomposition products on the propagation of brittle fracture in steel by means of electron microscopy. Newly developed replication techniques together with the advantages of the electron microscope such as great depth of field, available high magnification and easy adaptation to stereophotography make electron microscopy very suitable for fracture studies. EXPERIMENTAL PROCEDURE An essentially plain carbon steel containing 0.56 pct C, 1.30 pct Mn, 0.02 pct P, 0.03 pct S and 0.22 pct Si was used in this investigation. The following table gives the heat treatments used to obtain the various austenite decomposition products: The resulting austenite grain size from the 870°C austenitization treatment was about an ASTM No. 7 grain size. The specimens which were 2 in. long, 1/4-in. diam bars were austenitized in a tube furnace through which argon gas was blown. The tube was not, however, air-free and the specimens were not completely oxide-free. Isothermal treatments were done in a lead bath. With the exception of the fully hardened specimen and the one as-isothermally transformed at 300°C the heat treated specimens were notched in the following fashion with a jeweler's saw. A cut about 0.08 in. deep was made perpendicular to the length of the bar. The specimen then was rotated about 45 deg and another cut about 0.08 in. deep was made. In the case of the hard martensitic and bainitic specimens, only one cut was made and the depth was not controlled. The design of the two-cut notch caused fracture to initiate at the point of intersection of the two saw cuts. The specimens were broken at -196°C in a Charpy impact testing machine. In order to hold the specimens securely in the impact machine two square pieces of mild steel were made about 5/8 in. long having the same cross section as that of a standard Charpy specimen but containing a hole 1/4 in. diam through the center of the cross-section. These adapters were slipped over the ends of the test specimen which was then secured tightly by means of set screws in the adapters. The specimen with the adapters was cooled to -196°C in liquid N,, then placed in the impact machine and broken within 3 sec. One half of the broken specimen was used for the electron microscope study of the actual fracture surface. The other half was nickel-plated and a cross section through the notch and fracture was polished for electron microscope examination. Carbon replicas of the fracture specimens for the electron microscope study were made essentially according to Bradley's evaporation technique.' Both direct carbon and two-stage carbon replication techniques were used. In the case of the direct carbon technique, a thin layer of carbon was evaporated first at an angle of about 45 deg to the mean fracture surface and then another film of carbon was evaporated normally to the fracture surface. The carbon replica was freed electrolytically.2 The specimen was made an anode in a 10 pct Nital polishing solution. It was etched intermittently by shutting off the power now and then. The freed replica was washed in 40 to 50 pct water solution of nitric acid for 10 min or so, then washed in water and picked up on a screen for examination. The two-stage carbon replication technique involved first making a primary replica of cellulose * acetate from which a carbon replica was then made. One side of a strip of cellulose acetate wet with acetone was pressed lightly against the surface of the specimen, allowed to dry and then stripped. Prior to the deposition of carbon, which was done at 90 deg to the cellulose acetate replica surface, chromium was evaporated at 45 deg. After the carbon evaporation the cellulose acetate was dissolved in acetone according to the Jaffe method3 leaving the carbon replica preshadowed with chromium for examination.

Jan 1, 1961

By E. W. Enqelmann

DURING January, 1933, burlap or coco matting was placed in the bottom of launders handling various products of the flotation plant of the Magna mill of the Utah Copper Co., with the hope of increasing the total recovery of gold. This was soon followed by placing various materials, such as coco matting, cotton twill, and common 10-oz. burlap on the bottom of the main tailing launder. The burlap was found to be the most economical material to use. The test was first conducted in an old wooden launder, 40 in. wide and 2000 ft. long, with 10-oz. burlap fastened

Jan 1, 1935

By R. S. Archer

SILICON is one of the most important elements in the metallurgy of aluminum. It is always present in small amounts in the ordinary grades of "pure" aluminum, and hence in all alloys made therefrom. Within the last few years binary alloys containing up to 13. per cent, of silicon have come into extensive use for castings. Silicon is also added, beyond the amount present as an impurity, in alloys containing one or more other elements such as copper, manganese, magnesium and nickel. The binary aluminum-silicon alloys are not yet heat treated to any extent in commercial practice, although, as will be shown, their properties are affected to a very considerable degree by heat treatment. There are other aluminum alloys that develop higher strength, but the special characteristics of the silicon alloys may well lead to the application of heat-treating processes on a commercial scale. The role of silicon in the heat treatment of aluminum alloys is more important than would be indicated by consideration of the binary alloys alone, because many of the alloys that are heat treated in regular commercial practice contain some silicon in addition to that derived from the aluminum ingot as an impurity. Among these may be mentioned the heat-treated 195 alloy castings, and the wrought alloys 258, Special 178 and 51S of the Aluminum Co. of America, and the German wrought alloy, Lautal. It is the purpose of this paper to present the results of experimental work and the conclusions derived therefrom regarding the heat treatment of the binary aluminum-silicon alloys. The products heat treated included forgings, chill castings and both "normal" and "modified" sand castings.

Jan 1, 1927

By Wilford Stork

CERTAIN influences of oxygen on iron have been known for many years and it has always been considered one of the worst enemies of the iron and steel founders. Nobody had a good word for it, hence little was done to make use of this oxygen. In all the fields of foundry practice, the desideratum was "melt without oxidation of the metal." In the consideration of the influence of oxygen on cast iron, we must not confuse this condition with oxidized iron caused by poor melting conditions, due to a high bed, heavy charges, low coke ratio, excessive melting rate, high blast, or poor charging. It is admitted that oxygen absorbed by iron melted under these conditions has a deleterious effect on the properties of the iron. The writer has had experience both in the melting under such poor conditions and in remedying these bad conditions and considers the product far inferior to iron melted under normal conditions. As stated by Dr. Richard Moldenke,1 such iron has a higher melting point and high combined carbon, is sluggish, and contains slags and oxides in solution in the liquid, causing slag inclusions and gas occlusions, thus producing defective castings. This oxidized condition cannot be counteracted or removed by any of the known deoxidizers; it can be remedied only by proper melting conditions. Such iron is really burned, whereas the iron considered in this paper was melted under normal conditions with moderate blast, correct bed height, light charges of iron, and low coke consumption and is not in this category at all. In 1914, the late J. E. Johnson, Jr., startled the metallurgists of the world when he published his results on the advantages of oxygen on cast iron.2 His work is so convincing and so logical, in spite of the common and well-established notions on the subject, that nobody has been able to refute a single argument. Such an eminent authority on iron and steel metallurgy as Prof. H. M. Howe has accepted the work in all its details in his latest book3 The work of J. E. Johnson, Jr., has revolutionized

Jan 6, 1919

By A. A. Bauer, F. A. Rough, G. H. Beatty

AS a result of recent studies, the constitution of the zirconium-uranium system has been fairly well defined. A diagram for the system is shown in Fig. 1. However, both oxygen and nitrogen are known1-3 to have a pronounced effect on the limits of both ß- and e -phase regions. It has been shown that small amounts of oxygen severely constrict the compositional limits of these phase regions in the ternary zirconium-uranium-oxygen system. A previously published tentative diagram shown in Fig. 2 illustrates the ß-phase constriction resulting from oxygen additions. Generally, iodide zirconium has been used in constitutional studies of zirconium-uranium alloys. While this is the highest purity material available, cast iodide zirconium-uranium alloys will generally average from 200 to 300 ppm 0 and from 50 to 60 ppm N. Thus, while the constitution of the zirconium-uranium system is fairly well defined, it must be realized that this definition applies to alloys containing in the vicinity of 250 ppm 0 and 50 ppm N. The present investigation was undertaken to accurately determine the boundary between the ß-plus-P and ß phases at a single temperature in the binary zirconium-uranium system by quantitatively

Jan 1, 1959

By W. J. PRIESTLEY

WHEN during the war the Navy Department decided to build an armor-plate and gun-forging plant of its own at South Charleston, W. Va., one of the most important units of the equipment proposed was a 14,000 gross ton forging-press to be used for forging, bending, and rectifying battleship armor-plate and making hol¬low forgings for large caliber guns. A press suitable for doing this kind of work was put into operation in the fall of 1921 and was operated successfully on armor-plate and large forgings until the closing down of the ordnance plant following the Limitation of Armament Conference held in Washington, February, 1922. PURPOSE OF THE PRESS There are three methods by which armor-plate can be made, namely, hammering, forging, and rolling the ingot. Each method produces a different result in the mechanical working of the steel. The hammer was eliminated as impractical from an operating standpoint. The first armor-plate made in this country was worked under a hammer at the Bethlehem Steel Co., between the years 1891 and 1893, but was superseded by forging when the large press was completed in 1893. Harry T. Morris of the Bethlehem Steel Co. informs me that the 1.25-ton steam hammer began operations in 1891 and was in operation for about two years. The Carnegie Steel Co. and the Midvale Steel and Ordnance Steel Co. also forged armor-plate. Certain European manufacturers rolled the plates from large slab ingots, after removing the sink-head and giving the body of the ingot a light pass under a hydraulic press. While rolling accomplished more mechanical work on the surface of an armor plate, forging, on the other hand, resulted in a greater amount of work in the interior of the plate. Either type of equipment involved an enormous expendi¬ture, so it was deemed advisable to adopt the method which would make it possible to use the equipment for more than one purpose. Since g large rolling-mill could be used only for the single operation of rolling armor-plate, a press was decided on, for the reason that it might be designed so as to forge armor, as well as bend and rectify it, and also be used in the forging of ingots for large caliber guns, both in the form of hollow forgings and also solid shafts.

Jan 1, 1926

By D. Swan

Industrial research may be defined as a critical and exhaustive investigation to create new and better ways of doing things. The results of industrial research are new and improved products, processes, and techniques. This broad definition, of course, covers investigation of all subjects by either individuals or groups of people, and this chapter aims to examine the purpose (what research tries to do), and methods (or how research is done) as applied in the mineral industries. Concepts and History The idea or concept of organized research probably originated in the universities of Europe. There, groups of scholars banded together for discussion and application of their particular specialty to a common problem. Publication of the conclusions drawn from such investigations gave scholars in other areas the opportunity to review and criticize the work of their colleagues, and one of the hallmarks of scientific research work is the publication and criticism of the results of the investigation. It was not until the late nineteenth century that the concept of organized research for the profit of industry was recognized. During the late nineteenth and early twentieth centuries, a large number of industrial enterprises sponsored organizations to study the application of the physical sciences with the aim of making discoveries that would result in profit to the sponsoring organization. The tangible benefits accruing from these activities were so great that they, in turn, fostered several other methods for the support of organized research activities. For the large problems involving public interest, United States Government scientific re- search laboratories were set up. As the demand of smaller enterprises for research activities increased, research institutes and consulting laboratories were organized. In Europe the idea of common industry sponsorship of research centers grew and many large research organizations there were sponsored by associations of manufacturers. Finally, in the United States

Jan 1, 1959

By Franklyn Oatman

IN order that the conditions which obtain in an oil well may be readily understood, a brief description of a typical California well and. a number of the phenomena accompanying same will be given. That the necessity for the exclusion of water be realized, the effects of water intrusion, a description of methods of prevention, and a discussion of causes of failure will be presented, followed by a summary and recommendations. Fig. 1 shows a section of a typical well which illustrates the relation of oil sands to overlying strata. It indicates a deep water sand separated from the oil sand by shale, and the proper place for the final shutting off of water. In this well a comparatively thick stratum of compact shale protected the oil from overlying water so that the operation of landing the water string was a simple matter. In some wells the protecting stratum may be only from 3 to 5 ft. thick and very careful operation is necessary in order to land the water string of casing properly and not puncture through to the oil sand. The cases just cited are common, but occasionally, after excluding overlying water, productive oil sands are drilled through in the expectation of finding more productive underlying sand, and a water-bearing stratum is tapped. In this case the problem is the reverse of the normal; water must be prevented from ascending rather than descending. A discussion of well-drilling methods is not within the scope of this paper, except such operations as pertain to shutting off of water. A brief outline of the several conditions which may accompany drilling follows. Some or all may be present in any particular case. The direct relation of these to prevention of intrusion will he discussed in detail further on. In drilling, the hole. becomes more or less irregular in shape, and rough, and as the casing follows the bit into the well it does not fit snugly against the walls. As a result, water may descend between the casing and walls of the well. If a circulation pump is not used during drilling, the hole is simply punched through and the pulverized material removed from the well by means of a bailer. If circulation is maintained there is a continual flow of water down inside the casing and up around the outside between the pipe and the walls of hole. This keeps an open. space around the pipe.

Jan 3, 1914

By RUSSELL C. FLEMING

THE important advances that have been made of recent years in mining and milling methods and in mechanical equipment at mines need no re- telling, but there has been a remarkable growth in one type of equipment which has gone nearly unnoticed. That is the increasing use of storage-battery locomotives underground. Since the war the number of these locomotives and their field of use have increased tremendously; their growing acceptance represents an al- most complete reversal of opinion from an earlier period when they were generally looked upon as in- adequate for the strain of mine service. At the time when storage-battery powered units were first making their bid for recognition, the use of power in haulage had already passed through several phases; hand tramming, rope haulage, compressed air locomotives, even gasoline locomotives, had all been used, ending finally in the general adoption of the electric trolley locomotive for practically all power-haulage requirements. It was, and is, conceded that the trolley loco- motive met more adequately the varied and severe conditions of mine service than any previous type of haul- age unit. Subsequent developments have had to endure comparison and surpass in performance that type of haulage before changes would be considered.

Jan 1, 1930

By Norman Pilling

The effects of lead and tin up to maximum contents of about 0.1 per cent. each, in the presence of oxygen between 0.04 and 0.30 per cent., have been studied. Tin is retained efficiently in the oxidized condition, whereas lead is not. An approximate relation between the lead-oxygen and tin-oxygen contents is deduced which, if observed, permits the presence of these elements without detrimental effect. Excess of lead beyond this limit affects ductility and rolling properties adversely and an excess of tin correspondingly diminishes the conductivity. It is shown that copper carrying a combined lead and tin content of several hundredths per cent., yet fully equal in quality to electrolytic wirebar, may be produced under commercial conditions. TIN is not normally found in more than bare traces in current grades of American electrolytic copper, and lead is rarely found to more than a few thousandths per cent. In the electrolytic refining of copper these metals do not present great difficulty in separation and their presence in any considerable amount in copper that has been refined by this method need not be tolerated. On the other hand, the effect of these elements is not entirely academic, as a considerable tonnage of scrap copper liberally contaminated with them has been reclaimed by the fire-refining process into metal with a residual lead and tin content of several hundredths per cent., yet having excellent working properties and fully equal in quality to current grades of electrolytic wirebar. Such copper has been found entirely suitable for use in the manufacture of electrical apparatus. In the absence of oxygen, tin is known to depress the conductivity rapidly, and lead to impair ductility and the rolling properties, yet the effects of these metals on commercial grades of copper-i. e., copper containing from 0.03 to 0.10 per cent. of oxygen-apparently has not received systematic attention. Occasional reference is made to the fact that in the presence of oxygen lead may be tolerated, yet Addicks says,1 in regard to overpoling: "The unstable condition can be controlled by adding certain substances, notably lead, in small quantities, but as mere

Jan 2, 1926

By Persifor Frazer

At a time when all those interested in the iron trade are carefully scanning the horizon for new sources of the raw material, a few words concerning a field, which though not new, has not been hitherto fruitful of statistical information, may be deemed appropriate at this meeting. The district alluded to is the belt of the Middle James River, or in other words, that portion of the ferriferous belts of Virginia lying between Josua Falls and the little settlement of Norwood, in the counties of Amherst and Nelson, and on the left bank of the James River. This region shows unmistakable signs of developing a very considerable market for iron ores and for iron in the future, as well as a tempting appearance of possible productiveness in the former. It, is extremely hazardous to deal in generalizations as to the productiveness or non-productiveness of these measures without a more thorough development than has yet been attained. It is true that they probably constitute an horizon whence comes a part of the marvellous mineral wealth of the northern peninsula of Michigan. But

Jan 1, 1883

By Leonard Grimshaw

THE idea of bonding two dissimilar ferrous metals, and making use of both, is an old one. Tips have been brazed onto tool shanks for many years. The bonding of larger pieces to form whole bars and sheets has also been accomplished, but has received little attention in the technical literature, although a number of patents have been issued covering various methods for its accomplishment. There are three main motives behind the manufacture of composite steels. One is that the physical properties of one steel may supplement those of another; a useful, but at the same time, hard, brittle steel may be backed by a soft ductile one, or a stainless steel may be backed by a steel possessing greater strength. Another motive is direct lowering of cost; an expensive steel may be backed by a less expensive one, bringing down the cost of the piece as a whole. The third motive is an indirect lowering of cost, as when a useful steel is backed by a steel that is easier to machine, so that machining cost on a finished product is lowered considerably. Often more than one of these motives lead to a decision to use a com-posite steel.

Jan 1, 1936

By H. T. Hildage

Although Greater New York does not bear any resemblance to a great mining district, the mining operations that are being conducted in and about the city are both extensive and interesting in character. With regard to the extent, it may be mentioned that, at present, there is more dynamite used in New York than in any mining district in the United States; that there are under construction about 38 miles of tunnel, and that 66 miles more are projected, most of which must be constructed .in the near future; that since 1903 at least 2,000,000 tons of earth has been removed in underground work, in addition to about 3,500,000 tons that has been removed in open-cut in connection with tunnel-work, and many times this quantity that has been removed in excavating foundations for buildings not connected with tunnel-work; and that there are to-day probably more than 5,000 men engaged in mining-work in and about New lrork City. These undertakings include almost every operation connected with underground work, from exploration by means of trench and boring, to the sinking of large shafts and the driving of large tunnels through every kind of ground from hard rock to soft, semi-fluid silt and quicksand. It is proposed in this paper to give a general description of some of the methods and appliances used in the opening-up of a " mine " in a large city, and a brief description of some of the &'mines" now being developed in New York, connecting as far as possible the methods described with the particular work for which they were designed, in order to give a general idea of the

Jan 1, 1908

By G. Das, S. V. Radcliffe

The substructural features developed in tungsten as a function of annealing temperature (up to 2200°C) and type of material [undoped and doped powder metallurgy (PM) tungsten and electron beam melted tungsten] have been investigated by transmission electron microscopy. For doped PM tungsten wires, characteristic "par-ticulate" substructural features developed rapidly with increase in annealing temperature above 700°C. The features consisted of parallel rows of elongated or circular shapes (500 to 1000A diam) lying along the direction of the wire axis and were identified as internal voids by diffraction contrast experiments. In recrystallized doped PM rod, larger voids were observed and were identified by precision dark field analysis to be cubic in shape and bounded by (100) planes. In marked contrast with both the doped PM materials, recrystallized undoped PM rod exhibited only very occasional and randomly arranged voids. Furthermore, no voids were observed in either material after electron beam melting. The high concentration of voids in the doped PM materials is attributed primarily to vaporization of doping additions or their pvoducts situated at the original grain boundaries , whereas the few voids in undoped material are considered to be traces of microporosity which were not eliminated during sintering. A tentative mechanism is suggested for the dezlelopment of the voids in relation to the processing sequences (sintering and working) and to the subsequent annealing. In recent years, a characteristic substructural feature consisting of rows of small elongated or circular regions of light contrast lying along the direction of working has been seen in thin foil electron microscopy studies of annealed sheet, wire, and rod tungsten. These features were present in the published micrographs of sheet by Weissmann et al.1 and of wire by Meieran and Thomas2, although the authors did not draw attention to them. Wronski and Fourdeux3 observed similar features in sintered rod tungsten (it was not specified whether or not the material was doped*) and interpreted them on the basis of their ap- particles, based on extraction replica evidence from the fracture surface of the initial hot-rolled slab material from which the sheet was prepared. No diffraction contrast experiments on the features were reported in any of these studies. The present investigation was undertaken with the primary objectives of: a) identifying the nature of these substructural features in tungsten by electron diffraction contrast experiments, since the contrast for voids can be expected to differ from that for crystalline or glassy particles, and b) elucidating the origin of the features and their development. For the latter purpose, doped and undoped powder metallurgy tungsten was obtained as rod and wire to represent different stages of reduction during final processing. These materials were examined both in the as-processed condition and after annealing to successively higher temperatures. In addition, the same doped and undoped materials were examined after vacuum melting in rod form. I) MATERIALS AND PROCEDURE Doped powder metallurgy (PM) tungsten wire (commercial purity 99.9 pct W) was obtained in the as-drawn and surface ground condition (0.030 in. diam "ground seal rod"). Doped and undoped tungsten rod (0.075 in. diam) representing an earlier stage of final processing was obtained from the same commercial source (Refractory Metals Division, General Electric Co.). Lengths of both the doped and undoped rod materials were single-pass melted in an electron-beam zone refiner to examine the effect of vacuum melting on the substructure. Annealing was carried out in a tungsten crucible in a tantalum strip resistance furnace under a vacuum of l0-15 mm Hg. Longitudinal sections of the wire and rod materials were examined by light and electron microscopy. The preparation of thin foils suitable for electron transmission from 0.030 in. diam tungsten wire and the rod specimens was carried out by means of a high-precision microjet technique developed to provide lack of jet stability and precise control of the area thinned. The method is described in detail elsewhere.' The foils were examined in a JEM 6A electron microscope using a goniometer stage (±20 deg tilt, 360 deg rotation) and operated at 100 kV. To minimize contamination problems a 200 µ condenser aperture was used in conjunction with a useful beam current of 50 µA. II) RESULTS AND DISCUSSION A) Diffraction Contrast Analysis. In order to determine the optimum conditions for the development of the substructural feature, a series of isochronal 30 min annealing experiments were carried out on specimens of the doped PM tungsten wire. The transmission electron microscopy analysis showed that the as-drawn wire, Fig. 1(a), consists of 'fibers' whose long axis is closely parallel to the wire axis of (110). The fiber width averages some 0.5 µ. Dense disloca-

Jan 1, 1969

By Albert Brokaw

THE so-called ?paraffin dirt" of the Gulf Coast oil fields has been con¬sidered an indication of the possible presence of oil and gas, and not a few wells have been brought in solely on the basis of such evidence. In a sense, it may be empirically justified as evidence of the presence of oil or gas, though it cannot be said to be infallible. If the writer is correctly informed, its association with oil and gas was pointed out by Lee Hager some years ago, and while it is commonly mentioned by geologists and operators in conversation, no discussion seems to have found its way into print. The present interpretation is based on laboratory study rather than on field investigation, and is put forth with the hope of stimulating discussion which shall lead to more complete understanding. The term "paraffin dirt" has been applied to soils with a peculiar texture, which has been described' as "curdy" or "rubbery." When moist, the material breaks much after the fashion of "green" cheese. It is rubbery under compression, but does not resemble rubber in tenacity or cohesion. When dry, the material ranges from hard clods to a horny mass of high tensile strength. The shrinkage in drying is very great, especially in the hornlike matter. The moist material ranges in color from dark brown in the specimens rich in organic matter to grayish in specimens containing more inorganic matter. All of the specimens studied were readily attacked by molds, which in some cases grew in great profusion on the samples. Samples exhibited a rather characteristic "swampy" or "mucky" odor when wet, and a characteristic odor of humic soils when moist.

Jan 4, 1918

By W. E. Keck, W. C. Lowry, G. C. Eggleston

The potential iron ores of Michigan can be classified from the stand-point of the predominant impurities into siliceous, sulphurous and phos-pllorous ores. Research on the flotation of each of these classes of ore was carried out in the following manner. The flotative properties of the valuable minerals of iron and of the worthless and deleterious ones were first determined under carefully controlled conditions. This information was then applied to synthetic mixtures of these minerals, which simulated the potential ores. Finally, data obtained during the two foregoing stages of the investigation were used in the flotation beneficiation of samples of the potential ores. Hematite is the most important mineral of iron in each of the above classes of iron ores. This paper deals with a study of that mineral in the very nearly pure state. There are two varieties of the mineral—specular hematite and massive hematite. The latter is the principal variety, but the former is an impor-tant' mineral of iron in some of the potential ores. Because of this condition, flotation research was performed with both varieties. This research consisted essentially of: (I) a survey of the literature on hematite flotation, (2) the preparation of pure massive hematite, (3) the preparation of pure specular hematite, (4) the development of a laboratory procedure and (5) flotation experimentation. For the purpose of this discussion, the results of previous work on the flotative properties of hematite can be summarized as follows: Specular hematite has been readily floated with terpineol and sodium oleate or heptylic acid1. Further, hematite has been likewise floated with a proprietary frother and oleic acid or other soluble oils2. Finally, lead nitrate, copper sulphate, silver nitrate, chromium nitrate, mercuric chloride, ferric

Jan 1, 1939

By G. C. Eggleston, W. E. Keck, W. C. Lowry

The potential iron ores of Michigan can be classified from the stand-point of the predominant impurities into siliceous, sulphurous and phos-pllorous ores. Research on the flotation of each of these classes of ore was carried out in the following manner. The flotative properties of the valuable minerals of iron and of the worthless and deleterious ones were first determined under carefully controlled conditions. This information was then applied to synthetic mixtures of these minerals, which simulated the potential ores. Finally, data obtained during the two foregoing stages of the investigation were used in the flotation beneficiation of samples of the potential ores. Hematite is the most important mineral of iron in each of the above classes of iron ores. This paper deals with a study of that mineral in the very nearly pure state. There are two varieties of the mineral—specular hematite and massive hematite. The latter is the principal variety, but the former is an impor-tant' mineral of iron in some of the potential ores. Because of this condition, flotation research was performed with both varieties. This research consisted essentially of: (I) a survey of the literature on hematite flotation, (2) the preparation of pure massive hematite, (3) the preparation of pure specular hematite, (4) the development of a laboratory procedure and (5) flotation experimentation. For the purpose of this discussion, the results of previous work on the flotative properties of hematite can be summarized as follows: Specular hematite has been readily floated with terpineol and sodium oleate or heptylic acid1. Further, hematite has been likewise floated with a proprietary frother and oleic acid or other soluble oils2. Finally, lead nitrate, copper sulphate, silver nitrate, chromium nitrate, mercuric chloride, ferric

Jan 1, 1939

By W. D. Kruger

Methods for analyzing flooding or cycling projects by means of two-dimensional flow calculations are presented in the literature. The use of these methods allows the determination of optimum operating conditions for such projects and provides information on pattern efficiencies, relative flow rates, pressure distributions and floodout histories. The accuracy of such analyses depends on the basic reservoir data employed, especially the absolute permeability distribution in the reservoir; however, absolute permeability data normally are determined from well flow tests and/or core measurements and are so limited in quantity and quality that they do not adequately describe the reservoir flow properties. A calculation procedure is presented for determining the areal permeability distribution in the reservoir. Use of the procedure allows verification of the basic reservoir data through the matching of past reservoir conditions, thereby providing proper data for reliable predictions of future operations. The calculation procedure is a numerical technique based on a mathematical model of the reservoir and is designed for solution by means of an electronic digital computer. Results from field application of this procedure are presented. Permeability distributions from measured data are compared to those calculated to indicate the need for the analysis. Comparisons of field-measured and calculated pressure distributions are given to establish the validity of the calculation procedure. The conclusions of this paper are (I) use of the calculation provides data that allow a match of past reservoir conditions and thus reliable prediction of future operations; and (2) the procedure should, where applicable, be used to provide adequate reservoir data for use in two-dimensional flow calculations and related reservoir analyses. INTRODUCTION One means of providing more precise engineering control over reservoir operations during all stages of depletion is to develop some type of model to simulate the reservoir, using information developed from the behavior of the prototype to predict the performance of the actual reservoir. The use of mathematical rather than physical models for this purpose has been gaining in importance recently because of the application and availability of electronic computers. Mathematical models avoid instrumentation difficulties and allow easier handling of large-scale problems. At present, analyses employing two-dimensional models are common, and thought is being given to the use of models in three dimensions. The use of multi-dimensional models is necessary to show not only what is occurring in the reservoir, but also where in the reservoir the phenomena of interest are taking place. Methods for analyzing flooding or cycling projects by means of two-dimensional numerical models are presented in the literature. The use of these methods allows the determination of optimum operating conditions for such projects and provides information on pattern efficiencies, relative flow rates, pressure distributions and floodout histories. The applicability of numerical models and the results of using such analyses have been presented through field examples. The references indicated here discuss fully the data necessary to build the mathematical reservoir model and the way the model is used to study or predict the future performance of the reservoir. The accuracy of the analysis of such projects depends on the basic reservoir data employed in the construction of. the model. In order to be sure the model represents the reservoir, it must be used to match some known set of reservoir conditions, i.e., to match past reservoir performance. The accuracy of the model is directly dependent upon the absolute permeability distribution in the reservoir; however, absolute permeability data are normally determined from well flow tests and/or core measurements, and are so limited in quantity and quality that they do not adequately describe the reservoir flow properties. There is always the need for better data and for verification of existing data. The purpose of this paper is to show the use of the mathematical model to match past performance in flooding or cycling projects, the use of numerical techniques to adjust the basic absolute permeability data if necessary so that a match is obtained, and in this way to generate the effective areal permeability distribution of the reservoir. A review of the basic concepts of the numerical model will be given, followed by a discussion of the data-adjusting technique for matching past performance. TWO field examples will be cited to show

By J. A. Jargon, H. K. van Poollen

Flow of slightly compressible fluids through porous media can be described by linear equations. Many mathematical solutions- are available for the boundary conditions of constant terminal pressures or constant flow rates, or a combination of both. Various techniques of formation evaluation use drastic rate changes, such as sudden shut-in. Other methods require that the well be produced at a constant rate. In practice, one is not always able m fulfill these rigid requtirements. This report shows a methor1 by which varying-rate data can be converted to a constant-rate pressure response, called the unit response function. After obtaining the unit response function, one may analyze it, using techniques described in the literature. The method uses tile principle of superposition. Necessary data is a time history of pressure and production. If pressure changes and/or rate changes are very drastic, the unit response function becomes erratic and oscillates The erratic and oscillating results are obvious, and under those circumstances, no answer can he obtained. It appears, however, that a response function without oscilla-tion will not contain any appreciable errors —- one gets either good results or no results. This report includes a mumber of examples of converting constant-rate data to constant terminal-pressure data and vice versa. In addition, a number of field-test applications are given. This method should be useful in converting mathematical solutions from one boundary condition to another. It already has proven useful in converting varying-rate data to constant-rate conditions. INTRODUCTION Pressure drawdown tests are performed on production wells to determine various reservoir characteristics, including permeability, distances to discontinuities, reservoir continuity and wellbore conditions. An ideal drawdown test is performed at a constant production rate with pressure observation during the drawdown period. A typical drawdown curve for a constant rate of production is shown in Fig. 1. In practice, a constant production rate cannot always be maintained. Fig. 2 shows a pressure drawdown curve for a varying rate. Usual methods of analysis are not applicable to tests such as this. It is, therefore, necessary to convert the varying-rate data somehow, before usual analytical techniques can be applied. This report describes a method of obtaining a response function. A response function can be defined as the relationship between pressure and time for a well producing at a constant unit rate. Such a response function can be analyzed by the usual analytical techniques. Hutchinson and Sikora' first approximated a resistance function (response function), and by applying the superposition principle, pressures were calculated using the varying rates. If no match was obtained, adjustments were made to the response function and the closer approximation was used again in an attempt to match calculated and observed pressure behavior. If a good match was obtained: the response function was then used to extrapolate the future aquifer behavior.

Jan 1, 1966