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By E. P. Abrahamson II

The effect of transition element binary solid-solution additions upon the recrystallization temperature of vanadium has been investigated. Cr, Fe, Co, Ni, Mo, Ru, Rh, Os, and IY lower the recrystallization temperature, while Ti, Mn, Zr, Cb, Pd, Hf, Ta, W, Re, and Pt raise it. The majority of elements have their greatest effect in less than 0.15 at. pet. Both the rate of change of recrystallization temperature with atomic percent solute and the limit of initial linearity are found to Correlate with the free atom grozdnd state outer electron configuration of the sollte element. THE work of Abrahamson and Grant1 and Abraham-son and Blakeney2 has shown that the solute's elec- tron configuration appears to be a prime determinant of both brittle-to-ductile transition and recrystallization temperature in dilute binary alloys. It has also been shown by Abrahamson3 that the limit of linearity, i.e., the limit of initial linear change of recrystallization temperature with atomic percent solute, is also a function of the electron configuration of the solute in iron base alloys. Because of the systematic nature of the solute electron configuration correlation, it is to be expected that some systematic variation might be observed upon changing the solvent. Thus, this study of recrystallization in vanadium base alloys is the first of a series aimed at defining the role played by the electron configuration of solute in determining the recrystallization characteristics of dilute transitional alloys. PROCEDURE All alloys were made using 99.8 pct V containing 0.011 C, 0.024 N, 0.08 0, 0.006 H, 0.035 Ta, and

Jan 1, 1962

By G. V. Raymor, James T. Waber, I. Rex Harris

The lattice parameters of a series of fcc alloys of cerium and thorium were measured at 93 " and 298OK. Lattice parameters were also estimated for 171OK. Substantial deviations, y, from Vegard's law were observed. Although y was negative at the two higher temperatures, it was positive and large at the lowest temperature. A variety of models, which have been proposed in the past, were considered, and the calculated values of y were compared with the observed values. The best agreement was achieved with values computed with Friedel's equation. THE purpose of this investigation was to determine the effect of temperature on the lattice parameter and on deviations from Vegard's law of Ce-Th alloys. A large negative deviation from Vegard's law was first observed independently by Weiner, Freeth, and Raynor' and Van vucht2 in the room-temperature lattice parameters of Ce-Th alloys that form a continuous series of solid solutions. This observation was confirmed by Evans and Raynor. The allotropy of unalloyed cerium was reviewed recently by Gschneidner, Elliott, and McDonald. In two subsequent papers,5" these authors reported the influence of various alloying additions on the y= transformation, which occurs below room temperature. Although other rare earths tend to stabilize the double-hexagonal phase, thorium, plutonium, and scandium as solutes tend to stabilize the normal fcc phase. With addition of sufficient thorium as a solute, there is evidence that the formation of is suppressed and it becomes possible to pass continuously with decreasing temperature from the room-temperature phase to the fcc a phase. Thus there is a closed loop which is similar in many ways to the y loop well-known in ferrous alloys. A closed field also occurs in the pressure-temperature "equilibrium" diagram of unalloyed cerium. Because of interest in the effect of thorium additions and their influence on the a and phases, lattice-parameter measurements were made at low temperatures on the fcc phase for a series of alloys ranging from 10 to 90 at. pct Th. The results obtained at three temperatures are shown in Fig. 1. Evans and Raynors analyzed the deviations from Vegard's law in Ce-Th alloys in terms of changes in the occupancy of the 4f electron level in cerium,

Jan 1, 1964

Jan 1, 1969

By G. F. Jenkins

ASBESTOS is a general term embracing the fibrous varieties of a number of minerals. Of these, the hydrous magnesium silicate, chrysotile (H4Mg3Si209), a variety of serpentine, is the most abundant and useful to industry. All other types of asbestos belong to the amphibole group of minerals and are classified as: crocidolite, NaFe(SiO3), FeSiO3; anthophyllite, (MgFe)SiO3; amosite, also a ferromagnesium silicate but with iron content higher than that of anthophyllite; tremolite, CaMg3(SiO3)4; and, actinolite, Ca (MgFe)3(SiO3)4. PROPERTIES The commercial value of asbestos depends largely on the physical property that permits it to be readily separated into fine filaments of high tensile strength and flexibility, which, coupled with the fact that it has the quality of incombustibility of a mineral-in distinction to vegetable and animal fibers-makes it of unique usefulness for many purposes. To some extent, the value depends upon the length of the fiber, although extreme length is neither necessary nor desirable for most purposes. Chrysotile occurs as cross-fiber veins, in which the asbestos fibers are approximately' at right angles to the vein walls, with vein width- or fiber length-seldom exceeding 2 or 3 in.; also as slip-fiber, in which the fibers 'lie in the same plane as the vein or on slippage planes. A cleanly broken vein of cross-fiber has a pearly luster and may range from a deep green or brown color to light shades of yellowish green or cream. When of good quality, the fiber filaments forming the vein may be easily drawn away from their neighbors and exhibit a fine silkiness and pure white color. They may be twisted into a thread and when flexed between thumb and fingers are found to be strong and pliable. Chrysotile withstands comparatively high temperatures without breaking down completely or fusing but begins to lose water of crystalliza-

Jan 1, 1949

By K. J. McGrew, J. W. Murphy

Introduction Maximization of profit consistent with environmental protection is the principal goal of new applications development for any conventional or in situ mining technique. Efficient evaluation of all the parameters that contribute to mining costs and production hinges on proper design and evaluation of testing programs and data. The program discussed uses several field and laboratory procedures to estimate ore deposit characteristics and optimize lixiviant compositions. Ore characteristics and lixiviant compositions are then used in a long path leaching test (stream tube test). Stream tube test data are analyzed by mathematical models with computer assistance to predict such wellfield rate parameters as target metal production, lixiviant consumption, and restoration. When these predicted rates are combined with market values for target metals, capital expenditures, prices of lixiviant chemicals, and other economic variables (labor costs, power rates, and licensing fees), an assessment of the relative feasibility of various proposed mining plans is possible. The flowsheet in Fig. 1 illustrates this process. [ ] Field and Laboratory Procedures In general terms, the procedures followed in the evaluation of an in situ leaching application aim at accomplishing: •rapid leaching and maximum recovery of the target metal in a marketable form, •low consumption of lixiviant chemicals, •unquestionably satisfactory restoration of the mined aquifer, and •minimization of capital and operating costs for the above through development of an optimum mine plan. Keeping these goals in mind, the following minimum test program is generally recommended. Geology •Estimate of ore reserves and their variability. •Average disequilibrium value for uranium deposits. •Ore thickness, depth to ore, water level, degree of confinement, and consolidation. •Characterization of quality and quantity of other ore deposit constituents (e.g. sulfide minerals, ion exchange parameters). Hydrology •Single well pump and injectivity test. •Downhole vertical permeability test to compare flow rates of barren and mineralized formations. •Groundwater quality as it may affect licensing, hydro metallurgy, and restoration. Hydrometallurgy • Flask or autoclave tests for optimization of lixiviant parameters and determination of specific reaction rate constants. • Flask or autoclave tests for assessing amenability of lixiviant solutions with ore, consumption of lixiviant, stability of metal in solution contacting ore, and environmentally important species mobilized. • A long-path leach test for modeling the behavior of the lixiviant solution flowing through a long mineralized streamline (stream tube testing). •Metal recovery tests from lixiviant solutions (ion exchange, electrowinning, etc.). •Lixiviant regeneration tests. •Environmental restoration tests.

Jan 1, 1985

By D. G. Russell

Two techniques have been developed with which the applicability of pressure build-up analyses can be extended to include pressure data which previously have been considered virtually unusable. One of the interpretation methods makes possible the analysis of pressure build-up performance during the wellbore fill-up or after production period which occurs soon after a well is closed in. The other technique is an extension of a method for analyzing pressure build-up performance during the late-time portion of the pressure build-up which occurs after boundary eflects first begin to alter the shape of a conventional pressure build-up curve. With both of these methods it is possible to obtain estitnates of the kh product, the skin factor and the reservoir pressure. In addition, with the late-time analysis technique it is possible to obtain an estimate of the contributory drainage volume of the well being tested. This means that in some cases a check on reservoir limit test and (or) material-balance calculations can now be obtained from pressure build-ups. Both methods are slightly more time-consuming than conventional pressure build-up analysis methods because trial-and-error plots of pressure data must be made. The late-time method for analysis of pressure build-ups is in principle applicable to the late-time portion of a two-rate flow test or a pressure drawdown test. The interpretation formulas and procedures for these types of tests are also outlined. In these cases, as with pressure build-ups, it is significant that an estimate of the contributory pore volume is also obtained. On the basis of limited experience with the new techniques, it appears that satisfactory estimates of the kh product, skin factor, reservoir pressure and, for late-time analysis, contributory drainage volume can be obtained. INTRODUCTION The analysis of bottom-hole pressure build-up behavior in closed-in wells has been a a subject of interest in petroleum engineering circles for many years. In fact, few other subjects have received as much attention as pressure buildup analysis methods have. The cause for this interest is essentially twofold in nature. First, the pressure behavior of a well can normally be measured with a reasonably high degree of accuracy so that good data for analysis can be obtained. Secondly, over a fairly wide range of operating conditions, valuable information as to the quality of the reservoir rock and completion efficiency of the well can be obtained at a nominal cost. In recent years, numerous papers have been prepared on the effects of various operating conditions and reservoir heterogeneities on pressure buildup behavior. Very little work has been done, however, on extension of pressure build-up analysis methods to those pressure data which are not amenable to analysis by the present methods. The theory upon which the analysis of shut-in bottom-hole pressure build-up data is based is derived from the solution of the radial flow equation for a slightly compressible fluid for constant-rate conditions. It requires that the well be closed in for a sufficient period of time to obtain a clearly defined linear portion on the plot of observed bottom-hole pressure vs log (t + ?t)/ ?t (where At is shut-in time, and t is producing time to the instant of shut-in). From the slope of the plot and other normally obtainable data, the formation permeability, the well damage or skin factor, and the reservoir pressure at infinite shut-in time (if the reservoir were infinite) can be estimated. The successful application of this procedure depends on being able to recognize the straight-line section on the basic pressure build-up plot. The presently used pressure build-up interpretation theory also assumes that a well is closed in at the sand face and that no production into the well occurs after shut-in. In practice, of course, the well is closed in at the surface, and inflow into the well continues until the well fills sufficiently to transmit the effect of closing-in to the formation. This adjustment period is commonly referred to as the "afterproduction" or "fill-up" portion of the pressure build-up. During the period that the well fill-up effect is most pronounced, the basic pressure build-up plot is nonlinear. At later shut-in times after the effects of a drainage boundary have been felt at the well, deviation from the straight-line behavior of the pressure build-up plot also results. In many cases either of these effects or a combination of both can make the straight-line portion on the pressure build-up plot difficult to recognize. Obviously, an extension of pressure build-up analysis methods to include the afterproduction period and the period in which boundary effects are being felt would be desirable and might render valuable pressure data which for years have been considered virtually unusable. The principal reference of note concerning pressure buildup analysis during the afterproduction period is a paper by Gladfelter, Tracy and Wilsey.1 In the approach of these authors it is necessary to measure the rate of influx into the well during the afterproduction period. This is done through sonic measurements or through measurement of tubing-head and casing-head pressures simultaneously with

Jan 1, 1967

By Alan Arias

On grinding in pure water, zirconium, tantalum, iron, and stainless-steel powders were extensively comminuted and simultaneously oxidized with hydrogen release, whereas nickel, copper, and silver powders did not react with water and their particle sizes increased. On grinding nickel, copper, and silver in water pressurized with oxygen, nickel and copper became extensively comminuted and were oxidized, whereas silver did not react with oxygen and its particle size increased. From these results and other considerations , it is hypothesized that for extensive comminution of ductile metals and alloys to occur on grinding they must react with the grinding media. UlTRAFINE metal and alloy powders are finding an ever-growing number of applications in metallurgy and in other fields.' Of particular interest are ultrafine metal and alloy powders suitable for dispersion strengthening.2'9 Various research programs on dispersion strengthening are being carried out and in some of these programs the ball-milling method is being used to produce dispersion-strengthened materials. This method usually involves the simultaneous grinding of metal or alloy and a dispersoid followed by consolidation of the resulting powder mixture. To obtain the ultrafine powders required for dispersion strengthening,' grinding is carried out in many liquids, including aqueous and nonaqueous media, with or without grinding aids.4'5 Nonaqueous liquids usually contain water as an impurity and some grinding aids may contain water of hydration.5 The water present may affect the grinding process. The writer has shown5 that. on ball milling chromium in water, the chromium is oxidized and hydrogen is released. It was surmised that the same reaction may occur on ball milling other metals and alloys in waterbearing liquids. Therefore, the investigation of ball milling in water was extended to metals and alloys other than chromium. In the course of the investigation, however, it became apparent that the data-to-gether with the results from a few additional experi-ments—could be used to postulate a comminution mechanism for ductile metals and alloys. A well-known comminution theory is that of smekal.7 According to this theory, comminution is possible because of the weakening effects of surface cracks and other imperfections in materials. This theory imposes a lower limit of about 1 µm for the ground particles. The beneficial effects of liquids and additives on the rate of grinding are well known.8 Mechanisms by which liquids and additives may aid in grinding were reviewed by Rose and Sullivan.' One aspect of these effects is based on Rehbinder's theory of crack propagation in materials under stress.9 According to Reh-binder's theory, liquids or additives may promote the spread of cracks in stressed materials by lowering the surface tension at the crack tip. Rose and Sullivan surmise that the same mechanism may be operative during grinding, thereby facilitating comminution of the particles. In addition, Rose and Sullivan reviewed how additives may act as dispersants as a result of their being adsorbed on the surface of the particles being ground. This concept has been suggested by Quatinetz, Schafer, and smea15 to explain from their experiments the major role of additives that enabled them to grind metal down to 0.1 µm. Discussions of other comminution theories and additional sources of material on the subject will be found in Ref. 10. None of these previous suggestions and theories, however, can account for all phenomena encountered during ball milling of metals to submicron size in this and in a previous investigation by the author.6 The objectives of this investigation were to determine the behavior of metal powders during ball milling either in pure water or in oxygenated water and to gain an insight into the grinding mechanism. Zirconium, tantalum, iron, nickel, copper, and silver powders were ball-milled in pure water. These metals were selected because their oxides cover a wide range of free energies of formation. For comparison purposes, an alloy-type 430 stainless steel-was also ball-milled in pure water. The pressure of the hydrogen released during ball milling was monitored in order to determine the oxygen that combined with the metal or alloy. In order to obtain more information on the nature of the grinding process, nickel, copper, and silver powders were also ball-milled in oxygenated water (water pressurized with oxygen). The oxygen that reacted with the powders was determined from the pressure decrease in the mills. The powders resulting from ball milling in pure water and in oxygenated water were subjected to surface area, optical microscopy, and X-ray diffraction analyses. With these data, the oxygen calculated to be combined with the metals during ball milling, and comparison of the free energies of formation of the oxides of the milled powders with that of water, a comminution mechanism was postulated. MATERIALS, EQUIPMENT, AND PROCEDURES The materials used in this investigation were powdered metals, deaerated distilled water, high-purity helium, and commercial grade (99.5 pct purity) oxygen. The powdered metals used were zirconium, tantalum, iron, nickel, copper, and silver. A 16 pct Cr, ferritic stainless steel, type 430, was also used. The purities (or nominal compositions) and the surface areas of these metals and the alloy are given in Table I.

Jan 1, 1970

By Carmine D. &apos, Lemuel Tarshis, Joel Hirschhorn, Antonio

Vapor-deposited nickel films in the thickness range 700 to 4360A were tested in uniaxial tension utilizing a microtester designed specifically for this study. Contrary to the findings of some investigators, a definite thickness-strength relationship was observed below 3000 A with a four-to sevenfold increase in strength over that of bulk nickel. The films were characterized by high elastic strains and little plasticity. On the basis of these and other reported data, it is suggested that the high strength level in metal films is related to the manner in which they are produced. Vapor deposition, owing to its severe quenching effect. is believed to promote the formation of point defects which inhibit dislocation movement. IN recent years it has been reported that metals, when in the form of thin films, exhibit extraordinarily high strengths. The data published to date have been primarily concerned with silver and gold because of the ease with which these metals can be vapor-deposited and their high resistance to surface oxidation. Previous investigations into the mechanical strength of thin films has uncovered an apparent dichotomy of view on film behavior. Beams and his co-workers have reported a definite dependence of strength on film thickness. Other workers,"-'6 however, in separate studies on the strength of poly crystalline and single-crystal films have found no such thickness-strength relationship. The study of thin-film strength is extremely difficult because of the many variables associated with film preparation, handling, and testing. Moreover, the manner of test employed by different investigators has varied quite radically, ranging from simple uniaxial-tension to biaxial-bulge testing. The work reported herein was conducted in order to determine the mechanical behavior of a structural metal when in the form of a vacuum-deposited thin film and to gain some insight into the reasons for the high strengths exhibited by metals having such a con- figuration. In this study a method of test was chosen which would yield results which are easily interpreted and lend themselves to comparison with properties of the same material in bulk form. Moreover, specimen-preparation parameters and film-handling techniques are set forth so that other investigators can properly compare their findings with ours. EXPERIMENTAL PROCEDURES A) Film Preparation. Vacuum deposition was performed in an 18 by 30 in. bell jar using a standard New York Air Brake Co. vacuum station with a 6-in. oil-diffusion pump. Before evaporation the system was pumped to a pressure of less than 2 x 10"5 torr. A shield was employed to protect the substrates from the emission of contaminants during the critical melting and outgassing of the evaporant. The source consisted of from one to six filaments (0.020 in. diam). The length of each filament was about 5 in. and was placed 6 to 8 1/2 in. from the substrate in such a manner that the substrate face was at 90 deg incidence with respect to the evaporant beam. The temperature of the source was 2000"~ during evaporation. The films were deposited onto a substrate arrangement which was composed of four basic components, that is: 1) a 3 by 1 in. glass slide; 2) a 22-mm sq micro cover glass on 1); 3) a 22 by 50 mm micro cover glass coated with collodion on 1); and 4) a stainless-steel sheet mask containing twelve rectangular openings of 1-mm and 2-mm widths and lengths of 5 mm laid over 3). Thus, test specimens of 1-mm and 2-mm widths are deposited onto a collodion substrate which precludes epitaxial effects in the specirnens. 17-le The rectangular cover glass and square cover glass were positioned in such a manner that a strip of film would be evaporated along the length and across the width of the large glass slide. This boundary of evaporated film was used to determine the film thickness by multiple-beam interferometry. The square cover glass was used for X-ray and chemical analyses. Thickness of the deposits was varied by changing the number of filaments used (one to six). The duration of evaporation was 30 sec for each filamgnt which resulted in a deposition rate of 8 to 20A per sec. Evaporations were all performed at room temperature; however, radiant heat from the source raised the substrate temperature to 40" to 60°C. All substrates were cleaned by ultrasonic agitation in a solution of spectranalyzed isopropyl alcohol. Collodion was deposited on the micro cover glass by immersion in solution of collodion in amyl acetate. B) Thickness Control and Measurement. Film

Jan 1, 1963

By J. A. Roberson, Robert A. Rapp

From the observation of platinum wire marker movement in the oxidation of columbium at high lemperatures and low oxygen pressures, predonzinant cation diffusion in CbO, has been demonstrated. The Cu,0 molecule was used as an oxidizing species to study the nature of the porous scale and the location of the reduction site in the oxidation of colum-bium. The Cb205 scale contains microporosity and forms by alternate ionic diffusional growth and fracture. The oxidation of columbium at high temperatures and very low po, results in a relatively compact and protective Cb205 layer. THE observation of marker movements during oxidation is one means for the identification of the mobile ionic species in an oxide lattice. Previous marker experiments in the oxidation of columbium have all resulted in the markers being found on the outside surface of the Cbz05 scale. The Cr203 powder markers of Klopp et a1.,' the gold film marker of Kofstad and ~jijllesdal,' and the platinum wire marker of Cathcart et a1 .3 were found at the oxide/gas interface for oxidation temperatures ranging from 450" to 120O0C. However, in all experiments relatively high oxygen pressures were used. As discussed by Mrowec, even the interpretation of marker experiments in simple scales containing only one compound is not without ambiguities. In brief, it can be said that a marker may be found almost anywhere in the scale layer if the metal oxidizes by cation diffusion through the scale; the position of the marker depends upon morphological happenings in the scale. When considering marker movement in a polyphase scale one must proceed with extreme caution. For example, in the past (and present) work markers have never been found at the columbium-scale interface, and one might infer that the oxygen ion is mobile in CbO and CbO,. However, only trace quantities of CbO and CbOz have been present on any of the specimens, so no firm statement is justified on this basis. Despite previous experimental work, considerable doubt still exists concerning the role of the oxides CbO and CbOz in the oxidation of columbium. The identification of the mobile ionic species in CbO and CbOz from the observation of platinum wire markers was one goal of the present investigation . The linear kinetics of columbium oxidation at high temperatures (T - 1000°C) suggests that the Cbz05 scales which form on columbium are porous. From mercury absorption measurements on a Cbz05 scale formed at 500"C, Aylmore et al.' reported a minimum volume fraction of connected voids equal to 0.15. While these scales often appear to be quite porous when viewed in metallographic cross section, they are so brittle that metallographic preparation is likely to exaggerate any porosity originally present. In this investigation, porosity developed during the oxidation of pure columbium and present at the high temperature was detected by oxidizing specimens in sealed evacuated capsules containing large compacts of mixed copper and CuzO powders. wooda has demonstrated that the CuzO, or (CuzO),, molecule is volatile and that oxygen is transferred by the CuzO molecule from a Cu/CuzO mixture to materials having a greater affinity for oxygen. For each molecule of CuzO that is reduced at a sink for oxygen, two atoms of copper are deposited. Quantitatively, essentially all of the oxidation carried out by a Cu-Cu20 compact results from a displacement reaction involving the CuzO molecule. When a metal which oxidizes to form a porous scale is exposed to the CuzO vapor, the CUZO molecules are reduced in the pores leaving a deposit of metallic copper to mark the site of the reduction. This technique has the rather unique advantage that any copper-coated pores found in the scale are unambiguously related to the reduction site in the growth of the scale under consideration. Pores or cracks which form in a msition*- external to the reduction site or which occur as a result of cooling or handling of the specimen will not exhibit the copper deposit. EXPERIMENTAL PROCEDURE Marker experiments were made on columbium metal, and on pellets of CbO which had been pressed and sintered. Platinum wire markers (0.001 and

Jan 1, 1968

By Maurice Grieves

The great majority of shafts constructed today are still excavated by drilling and blasting, a method which changed very little in over 100 years until the introduction of the mechanical lashing unit and cactus grab by the South Africans, which enabled muck to be removed as fast as massive hoisting systems could handle it and resulted in very rapid rates of sinking. Record breaking month's performances were achieved at -Hartebeestfontein No. 4 shaft, October 1960-337.1 m; Western Reefs No. 4 shaft, October 1961-340.7 m; and Buffelsfontein eastern twin shaft, March 1962-381.2m. The method was very labor-intensive, requiring a crew of over 60 workers at the shaft bottom during the drill cycle. Safety precautions were strict, but in the drive to achieve rapid advance, cases of personal injury were still somewhat high because of the large number of people engaged in this potentially hostile environment. The South African method, as it came to be referred to throughout the rest of the world, was adopted in the United Kingdom in the late 1950s in a modified form with greatly reduced manpower and nonsimultaneous sinking and lining, which was insisted on by the British Mines Inspectorate. In that instance, it was successfully used to sink the 7.3-m-diam concrete-lined shafts at Kellingley to 770 m depth, with rates of advance of over 90 m/month achieved, a British record at that time. During the sinking of the 1.15-km-deep twin shafts at Boulby potash mine in the UK in 1970, the method was again used, but for the first time ever in Britain exemptions from the mining code permitted the use of crash beams, crash doors, jack catches, and semi-simultaneous sinking and lining techniques. New British shaft sinking records of over 120 m/month were achieved in both shafts. Similar equipment and techniques were used in the early 1970s to sink several deep shafts in Canada, notably Creighton #7 and the Con zinc mine at Yellowknife in the NW Territories. Today, this equipment is standard for deep shafts in the US and the rest of the world. However, with the tremendous escalation in mining labor costs, the impact of health and safety legislation, and environmental regulations, coupled with a very real shortage of miners willing to work in this exposed situation it was apparent that an alternative to the labor-intensive conventional method of shaft construction had to be found. Recognizing the trend is inevitable, one or two major German shaft sinking contracting firms began to take a fresh look at full face boring techniques applied to tunnels and raise bored shafts. The results were most encouraging. Tunnel drivage techniques using moles had developed considerably from Colonel Beaumont's original channel tunnel machine circa 1880 to the superbly engineered Priestley machine selected to cut the British side in 1975 and the double shielded Robbins Grandori borer on the French side of the English Channel. Full face tunnel machines were being successfully used to drive uphill in inclined shafts in Austria and Switzerland. At Mapprag in Switzerland, the Demag mole drove the first (intentional) vertical transition and curve, and then went on to successfully complete the 730-m-long penstock shaft at an inclination of 35°. In Austria, the Wirth mole drove the Kaprun Glacier ski-lift railcar tunnel at record breaking rates of 457 m/MONTH (best 30 m/d) through green schist at an inclination of 29° for a distance of 3.35 km while the Hydro tunnel at Sarrelli in Switzerland was being driven by the Robbin's mole at an inclination of 35°. Simultaneously, extremely promising results were obtained using large assemblies of cutter discs on raise borer heads, such as the 4.87-m-diam X 460-m-deep shaft raised by Teton for Jim Walter Resources Inc. Bearing in mind that most mine shafts in the future (unless in exceptionally competent rock) will require some form of lining, and the trend will be toward deeper shafts as the more easily accessible mineral deposits become exhausted, it was seen that normal raise boring had definite limitations in vertical accuracy, in the limitation imposed by the drill string on the available torque that could be applied to the cutter head, and in the risk of collapse of the unsupported shaft rock wall in friable or jointed and fissured ground, since it is not possible to apply any form of temporary support until the permanent lining is being installed. A further problem was the economics of installing a subsequent lining, necessitating setting up a headgear and hoisting arrangement approaching in size that required for conventional drill and blast sinking and lining. Because of the economics, German contractors opted for a phased transition from drill and blast to the full face, rodless, out of the solid shaft mole, by starting off with a down-the-hole shaft boring machine -without a drillstring-but using a pilot hole to get rid of the muck.

Jan 1, 1982

By S. L. Lopata, E. B. Kula

A variation of yield and tensile strength with direction has been noted in heat-treated 4340 steel which had been warn-worked by rolling in the austenitic condition prior to quenching. Measurements by X-rays showed a preferred orientation of martensite crystals. Various ideal preferred orientations of martensite were calculated by assuming a preferred orientation for austenite and transforming this to martensite by the Kurdjumov -Sachs and Nishiyama relationships. Comparison with the measured preferred orientation showed that the ideal rolling texture for austenite in 4340 steel could be expressed as a (112) [111] texture with a component of (110) [112]. No evidence was found for any fiber axis in the rolling direction, or fop- a (123) [412] texture. The observed martensite pole figures can be adequately accounted for by these ideal austenite textures and by the Kurdjumou-Sachs or Nishiyama transformation relationships between austenite and martensite. ALTHOUGH preferred orientations are found in cold-rolled steel sheet and in many nonferrous metals, they are not generally encountered in wrought, heat-treated high-strength steels, since such steels are generally not cold worked sufficiently to develop a strong texture, and any texture that is present is removed during heat treatment by the phase transformations taking place. This report gives details on a preferred orientation found in warm-rolled and hardened 4340 steel. In a recent study, a special combination heat-treating and working technique was used in which 4340 steel was deformed in the austenitic condition, and before re crystallization of the austenite could occur, quenched to form martensite.' Since the austenite was unrecrystallized, it was cold worked and hence could have contained a preferred orientation which could be transmitted to the martensite on quenching, and this in turn could be manifested as a directionality of mechanical properties. Such a directionality of properties was found as a result of working, and this prompted an X-ray study of the preferred orientation. Literature Survey— Rolling Texture in Face-Cen-tered-Cubic Austenite—M a preferred orientation is found in a rolled and hardened steel, it is first appropriate to consider what texture existed in the austenite as a result of the rolling but prior to the transformation to martensite. The changes taking place as a result of the austenite-martensite transformation are then considered. In view of the instability of austenite in 4340 steel at low temperatures, no direct determination of the austenite texture was made. However, an estimate of the texture for austenite in 4340 steel may be made by considering the textures found for other face-centered-cubic metals. Barrett' has reviewed the rolling textures for many materials. The most common orientation in face-centered-cubic metals has the (110) planes parallel to the rolling plane and the [112] directions parallel to the rolling direction, or (110) [112]. Other orientations found are (112) [111], as well as (100) [001], (110) [001], and others. Beck and his co-workers, using quantitative pole figures, report that (123) [121],3 later corrected to (123) [412],4 better describes the ideal orientation. smallman5 reported that the ideal preferred orientation for high-purity face-centered-cubic metals is (123) [121], but that there is a transition to (110) [112] as solid solution elements are added. The latter texture tends to occur more readily at lower temperatures. This transition between the two textures was explained by differences in the slip characteristics with concentration or temperature. More recently, Jones and Fell6 concluded that the (123) [412] texture for face-centered-cubic metals could equally well be represented by a mixture of (110) [112] and (112) [111] textures, and hence it had no physical reality. From the above results it can be seen that there is no agreement on the "ideal" texture for fcc metals and, hence, no firm basis for assuming a texture for austenite in 4340 steel. Therefore, the orientations (110) [112], (123) [412], and (112) [111] have been considered in the following.* *The (123) [4121 is identical to the (123) [121] rotated 90 deg. Orientation Relationship between Austenite and Martensite—When martensite forms from austenite, certain crystallographic planes of the martensite are parallel to planes in the austenite. This orientation relationship was first determined by Kurdjumov and

Jan 1, 1960

By Thomas C. Wilder, Walter E. Galin

Measurements of the electromotive force of the cell at 995°C have shown that the cell may be used to detennine the zinc content of molten Cu-Zn alloys to the nearest 0.05 wt pct. The cell is used for brass melts to which no ZnO is added intentionally, because essentially all oxygen in the Cu-Zn-O system is present in the form of ZnO. The cell is also used to detev,nine the thernodynamic activity of zinc for Cu-Zn al1oys of the brass composition range, from which the equilibrium partial pressure of zinc for such alloy may also be calculated. The electrochemical measurement of the concentration of the most active metal in other engneering- alloy systems by a similar technique is also considered. IN recent years there have been many studies concerning the direct electrochemical measurement of oxygen content in molten engineering metals.' These investigations employ galvanic cells in which the electrolytes are various solid mixed-oxides which conduct current by movement of oxide ion vacancies under the influence of an oxygen potential gradient. Similar cells have also been used to measure the thermodynamic properties of mixing of solid alloys,' one component of which has a much greater affinity for oxygen than the other component(s). One alloy system of obvious engineering importance comprised of two metals of greatly differing affinity for oxygen is copper-zinc. At the casting temperature of molten brasses, the zinc concentration is very difficult to control not only because its vapor pressure is very high, but also because of its high affinity for oxygen to form ZnO. Inasmuch as brass castings may be required to have a zinc concentration within very narrow limits, it would be advantageous for the brass industry to have a means for quickly measuring the zinc content in the molten alloy just prior to pouring. A calculation based on earlier thermodynamic studies of oxygen and zinc in dilute solution in binary Cu-O and CU-Z' alloys indicates that the oxygen concentration of molten 70 wt pct Cu-30 wt pct Zn brass must be much less than 1 ppm for the separate phase ZnO not to exist in the ternary Cu-Zn-O system. Thus it can be assumed that all molten brasses, both in the laboratory and in the foundry, are sufficiently saturated with oxygen for the separate phase ZnO to be present. In view of the foregoing reasons, the cell investigated at 995°C for the purpose of measuring the zinc concentration in molten copper-zinc alloys, particularly those of brass compositions. In this cell the left hand electrode is a reference electrode comprised of a mixture of the pure powders of nickel and nickel oxide, to which a platinum contact is made. The electrode of interest is a molten Cu-Zn alloy of unknown zinc concentration with a tantalum wire contact. The electrolyte is the commercially available (Zircoa) calcia stabilized zirconia. The ZnO in the Cu-Zn electrode compartment is not intentionally added, but is naturally present as a result of the infinitesimal amount of oxygen required for its formation in this alloy system. In cell [A] nickel oxide is reduced at the cathode where O= represents the electrolyte. At the anode dissolved zinc of the Cu-Zn alloy is oxidized to form ZnO(s) in its standard state Thus the overall reaction is for which the molar free energy change is where 5 is the Faraday equivalent (23,063 cal per v equivalent), is the electromotive force of the cell in volts after correction for the Pt-Ta thermocouple, FOf (ZO) and AFF (NO) are the standard molar free energies of formation of the respective oxides, and a2n is the thermodynamic activity of zinc in the molten Cu-Zn alloy. The reference state of zinc in this case is taken to be the pure liquid. At constant temperature all the terms of Eq. [I] are constant except and azn Thus since all other participants in the electrochemical reaction are in their standard states, the change in the electromotive force of Cell [A] is represented only by a change of the thermodynamic activity of zinc at constant temperature. The zinc concentration is related to the activity by sampling the alloy for chemical analysis after cell measurements are taken. EXPERIMENTAL A typical cell construction is shown in Fig. 1. This and other experimental details were similar to that described earlier with the exception of some minor modifications which are detailed below.

Jan 1, 1970

The plans for the activities of the Petroleum Division for the coming year do not differ materially from those of the past several years. The fall meeting is scheduled for Oct. 12 and 13 and is to be held at Tulsa, Oklahoma. The Division, of course, will take part in the annual meeting of the Institute at New York. A fall meeting will also be held in California at approximately the same time as the meeting at Tulsa. A number of papers are to be presented at the two meetings simultaneously. The various committees are at work arranging the programs. The Division will continue to be active in its various fields of endeavor, such as stabilization, production reviews, and economics, but special stress is to be laid on the engineering and research fields. In the past the Division has served as a forum for open and frank discussion of problems confronting the engineers in the oil industry. It is hoped that it will continue to function in this capacity. Papers presenting original ideas and extending the boundaries of knowledge and understanding in the field of petroleum production will be welcomed. Members who have interesting information to contribute should not wait until called upon by one of the Committees, but should offer a paper at the earliest opportunity. The past year has seen a decided strengthening of the control over production, with prospects of even more rigid control in the future. It is essential that production programs under such control be carefully planned and it is highly desirable that petroleum engineers take an active part in the planning, to insure efficient production of oil and minimize the waste of this natural resource. At a time like this, when it is difficult to keep the production of oil within reasonable limits, it may seem unnecessary to improve the efficiency of production methods, but, as has been aptly said, the trouble is not that we have too great a reserve of oil but that we are producing tomorrow's oil today. Therefore it behooves those who are entrusted with the engineering and scientific phases of production to learn how to get the greatest yield economically possible from the present and future fields in order that we may enjoy the advantages of petroleum products for a long time to come.

Jan 1, 1934

By W. B. Finkeldey, C. H. Mathewson, C. S. Trewin

This paper was prepared upon request as a contribution to a symposium covering the manufacture, properties, and uses of the important non-ferraus metals. In approaching a subject as broad as this, there is a natural desire to build up a comprehensive and finished production which shall constitute a dependable source of information on all questions properly belonging to this branch of metal technology. There are, however, a number of circumstances, apart from the mere routine of labor and thought involved, which operate rather effectively against the possibility of completing such .an ambitious program at the present time. First of all, as far as any public record of results is concerned, the commercial rolling, drawing, and forming of zinc with relation to changes of structure and properties—and this we consider to constitute the clement~ of metal technology—might as well be an unpractised art. We have never seen a published photomicrograph showing the structural characteristics of either hard or soft sheet or strip, although the structure of castings has been frequently described, and other coarse-grained structures resulting from hard-hammering and annealing have been reproduced. Thus, an author in this field must proceed to his task without much assistance from the literature, and the outcome can represent only a personal estimate of principles, facts, or findings, and not a summary or survey of progress in the entire field as determined by varied experience, practice, and settled opinion.

Jan 1, 1921

By R. H. B. Jones

This paper reviews pertinent geology of the Biwabik iron formation, Mesabi Range, Minnesota. This iron formation is divisible into four members. Each member is distinctive and contains marker horizons, which are recog nizable throughout all phases of alteration from lean, fresh rock to high-grade iron ore. Some beds have a larger magnetite content than others. During the process of ore genesis, which is essentially an oxidation process, the magnetite content is lowered. Alteration from iron formation to ore includes both oxidation of iron minerals and silica removal by leaching and these distinct processes progress at variable rates for different locations and structures. Magnetic intensities, of each horizon of the iron formation are dependent chiefly upon its preoxidation magnetite content, upon the subsequent degree of oxidation, upon the character of the enclosing rocks, and on the extent of fracturing, folding, or faulting. The results of a number of magnetic surveys are described and are correlated with results of drill-hole and mine exploration and developmerit. The magnetic anomalies obtained are discussed in relation to phases of formation of ore within the iron formation. General Information One hundred years ago a party of surveyors, applying the principles of geophysical prospecting, discovered iron ore in the state of Michigan in the Lake Superior district. This event was officially reported as follows:' On Sept. 19 (1844) while running the east line of Town 47 North, Range 27 West, they observed by means of the solar compass remarkable variations in the direction of the needle, amounting to 87" from the normal. Ascribing this phenomenon to iron ore, they sought and found it in ledges or outcrops at several points. The solar compass referred to was invented by William A. Burt, deputy surveyor in charge of this party.2 It is used for determining the true meridian by an observation on the sun. Eight years later, on July 7, 1852, the first iron 're, consisting of 6 bbl. of Ore, was shipped from Marquette, Michigan. It was another 40 years before the first or> shipment left the Mesabi Range in Minnesota, in October 1892. It totaled 4245 tons. Fifty years later, 90 years after the original shipment, during 1942 the Lake Superior district shipped 93,495,392 gross tons of iron ore. Production came from Minnesota, Michigan, Wisconsin, and Ontario, Canada. Throughout the 90-Year period it was known that magnetic properties of most of the ore bodies, and of the iron formations in which they occur, affected the compass. This phenomenon, later to be made use of to outline areas of ground favorable for exploration, was at first a

Jan 1, 1949

By C. Chiou, D. P. Seraphim

The effect of clustering on the superconducting properties of Al-Zn alloys has been studied by the ballistic induction techniques. The superconducting critical temperature, T,, changes when zinc-rich clusters are formed. The change in T, depends on the concentration and may be positive or negative, but always correlates with an effective decrease in the solute concentration of the alloy. Reversion after clustering effectively returns a 5 at. pct Zn alloy to the quenched state. These methods might be use&lly extended to the Al-Mg system, where X-ray data are difficult to obtain. In very dilute Al-Zn alloys, as in other tin,' indium, aluminum,2 or tantalums base solid solutions, there is a decrease in the superconducting critical temperature, Tc, roughly proportional to the temperature independent resistivity, i.e., -0.2°K per pS2cm. With increasing solute concentration, the T, generally reaches a minimum and then increases4 to a value well above that for the pure solvent. The change of T, with solute concentration follows an empirical formulation involving two constants which correlate with the scattering cross section of the impurities. As will be shown below, the Al-Zn alloys more concentrated than 1or2at. pct do not follow the empiricism, probably because they are unstable even when rapidly quenched.5 However, it seems possible to study at least the later stages of solute clustering by precise measurements of the 1', following various thermal treatments. A few experiments on quenched alloys, aged alloys, and tests on reversion are reported here. The heat treatments selected for obtaining the quenched and aged states were mainly deduced from the work of Dash and Fine.6 For the quenched state, specimens were homogenized at 480°C, quenched to -160°C, and immediately transferred and mounted in liquid nitrogen. Measurements on the superconducting properties and residual resistivities were then made at helium temperatures, after which the specimens were aged at room temperature for 3 to 5 hr, i.e., much longer than the time required for clustering to be essentially completed. The superconducting properties and residual resistivities were once again examined. To reach the reverted state of the A1-5at. pct Zn alloy, the aged specimen was heated for 5 min at 200°C and then tested as above.

Jan 1, 1963

By R. H. B. Jones

This paper reviews pertinent geology of the Biwabik iron formation, Mesabi Range, Minnesota. This iron formation is divisible into four members. Each member is distinctive and contains marker horizons, which are recog nizable throughout all phases of alteration from lean, fresh rock to high-grade iron ore. Some beds have a larger magnetite content than others. During the process of ore genesis, which is essentially an oxidation process, the magnetite content is lowered. Alteration from iron formation to ore includes both oxidation of iron minerals and silica removal by leaching and these distinct processes progress at variable rates for different locations and structures. Magnetic intensities, of each horizon of the iron formation are dependent chiefly upon its preoxidation magnetite content, upon the subsequent degree of oxidation, upon the character of the enclosing rocks, and on the extent of fracturing, folding, or faulting. The results of a number of magnetic surveys are described and are correlated with results of drill-hole and mine exploration and developmerit. The magnetic anomalies obtained are discussed in relation to phases of formation of ore within the iron formation. General Information One hundred years ago a party of surveyors, applying the principles of geophysical prospecting, discovered iron ore in the state of Michigan in the Lake Superior district. This event was officially reported as follows:' On Sept. 19 (1844) while running the east line of Town 47 North, Range 27 West, they observed by means of the solar compass remarkable variations in the direction of the needle, amounting to 87" from the normal. Ascribing this phenomenon to iron ore, they sought and found it in ledges or outcrops at several points. The solar compass referred to was invented by William A. Burt, deputy surveyor in charge of this party.2 It is used for determining the true meridian by an observation on the sun. Eight years later, on July 7, 1852, the first iron 're, consisting of 6 bbl. of Ore, was shipped from Marquette, Michigan. It was another 40 years before the first or> shipment left the Mesabi Range in Minnesota, in October 1892. It totaled 4245 tons. Fifty years later, 90 years after the original shipment, during 1942 the Lake Superior district shipped 93,495,392 gross tons of iron ore. Production came from Minnesota, Michigan, Wisconsin, and Ontario, Canada. Throughout the 90-Year period it was known that magnetic properties of most of the ore bodies, and of the iron formations in which they occur, affected the compass. This phenomenon, later to be made use of to outline areas of ground favorable for exploration, was at first a

Jan 1, 1949

By Norris Johnston, Carrol M. Beeson

For many years the permeability of reservoir sands has been measured by flowing air through a cleaned and dried core sample. This differs from the true reservoir permeability in one important respect: the rock particles in the reservoir are surrounded by interstitial water, not air, and their physical shape and condition of hydration are greatly dependent thereon. Permeability as defined must be measured with a single-phase fluid. Since no means exist for removing the oil and gas from a core sample by simply flowing water through it, the sample must be cleaned and then resatu-rated with water before testing. The present discussion attempts to show that after the cleaning process a considerably different permeability is determined with salt or fresh water than is obtained with air. The postulate is made that the salt-water permeability is probably closer to the true reservoir permeability than is the measurement with air. This is discussed in relation to both physically possible and economically feasible measuremerits. Data On more than 1200 core samples are given to show the nature of the effects observed, and a plea is made for others to consider water permeability measurements as a routine necessity, eventually replacing air permeability in regions where the differences are great. Introduction Permeability is defined1 as a "a measure of the capacity of a porous medium to transmit fluids, when there is no interaction between the solids and the fluid." Darcy's law of liquid flow in porous media states: kA?P QµL/A?L [I] where Q represents milliliters of liquid of viscosity p centipoises passed per second through a porous medium of permeability k darcys and cross-sectional area A sq. cm. under a pressure gradient ?P/L atmospheres per centimeter, the flow being understood to be laminar or viscous, not turbulent. This equation defines the darcy. For the case of radial flow in a uniform sand, such as usually exists in the neighborhood of a well in an oil or gas sand, Darcy's law becomes:2 Here h is the net sand thickness in feet, Pe and Pw are pressures at the drainage radius4 and well radius, and re and rw are these radii, respectively. The productivity index3 is defined as the barrels of liquid produced per day per pound per square inch mean pressure differential between ferences and well bore, and is thus: By further definition, the specific productivity index is: or in terms of practical units, and allowing for shrinkage:

Jan 1, 1945

By M. H. Waxman, M. Gondouin, H. J. Hill

Streaming-potential experiments were conducted within the Muddy- and Dakota-sandstone interval of a Denver basin well. Analysis of the data shows that, for this case, streaming potentials opposite sands were higher than those opposite shales when the mud was fresh. Streaming potentials opposite shales, however, were of sufficient magniiIlde to be important in SP interpretation. They were linearly dependent upon pressure differential, and they increased with mud filtrate resistivity. The magnitude of streaming potentials opposite sands was influenced by the characteristics of the original mud cake formed at the time of drilling. Use of mud samples taken at the time of logging may not always be satisfactory for determining streaming-potential corrections. Both the streaming and electrochemical potentials were found to be affected by the previous history of the borehole system. Following a change in mud characteristics, several days were required for SP stabilization. This was, in part, due to the mud cake acting as an imperfect shale membrane. INTRODUCTION Laboratory investigations by Wyllie,1 Salisch,2 Moore," Sen Gupta and Bannerjee,0 and Hill and Anderson' have shown that streaming potentials developed across mud cakes deposited on permeable filter beds are of sufficient magnitude to be critically important in SP interpretation. Streaming potentials across shales have been reported by Schenck,' Gondouin and Scala; and Hill and Anderson." The magnitude of the shale streaming potentials obtained by Schenck and by Gondouin et a1 led these authors to conclude that in many cases the shale streaming potential would approximately equal the mud-cake streaming potential. Hill and Anderson, however, obtained somewhat lower magnitudes of shale streaming potential. The field experiment described in the present paper was a cooperative project carried out by the respective operations and research departments of Schlumberger Well Surveying Corp., Shell Development Co. and Shell Oil Co. The primary objective of the experiment was to determine in the borehole the streaming-potential behavior of both shales and mud cakes under conditions approaching, as nearly as possible, those normally encountered in logging practice. METHODS AND EQUIPMENT WELL A Muddy- and Dakota-sandstone vie11 in the Denver basin was chosen for the experiment. Both sandstones were water-bearing and, since reservoir pressures in these sandstones are abnormally low (gradient of approximately 0.25 psi/ft), it was expected that studies of streaming potential could be conducted from low-pressure differentials (approximately 200 psi) to about 27000 psi by bailing mud from the hole, filling up and then applying wellhead pressure. The selected well encountered the Muddy sand-

By J. R. Campbell

A dozen years or so ago, the general superintendent of our company, now the president, Mr. W. H. Clingerman, asked me to study the coal-washing problem. This work brought me into contact with the best washery men of the country. I investigated many kinds of coal-cleaning schemes, made numerous tests, and collected voluminous data, yet I confess frankly that I have had little practical washery experience and that little has been at the Middlefork washery of the United States Fuel Co. at Benton, Franklin Co., Ill., which was put in operation last fall. While this washery installation may not be the "last word," I am quite sure it embodies some long steps in advance of the older designs and constructions. From the washery man's standpoint, the removal of pyrites or marcasite, a disulfide of iron, is the one vital problem, and the one productive of the most beneficial results, so far as elimination of sulfur is concerned. Sulfates and so-called organic sulfur occupy quite a sec-. ondary position and are generally lost sight of in coal washing. The elimination of sulfur in coal in the past has usually been accomplished by jigging in water, but lately concentrating tables have been successfully employed. The flotation process has been applied to fine coal, but is hardly considered practicable. Coal washing is rapidly coming into its own, due to the depletion of low-sulfur coals for coking purposes, and we predict that soon the same careful attention will be given to the design and construction of coal washeries that is now being given to byproduct plants and other allied industries. Heretofore, coal washing has been considered only an incidental and necessary evil instead of the big problem it is—one worthy of the most careful study by men well trained along technical lines and capable of delving into the fundamental principles. Preparation oF Coal It is usually necessary to crush the mine-run coal before sending it to the jigs, the degree of crushing depending on the occurrence of the sulfur and other impurities in the coal and the type of jig over which it is to be sent. The feldspar jig requires finer and more uniform crushing

Jan 1, 1920