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By H. Hubert

The first attempts at direct utilization of blast-furnace gas in engines were made in 1895. For a considerable time the gas had been burnt in Cowper stoves for heating the blast for the furnace, and under the boilers which supplied steam to the blowing-engines, and others serving the furnaces. It was natural, therefore, that the idea of directly employing it in gas-engines should have occurred simultaneously to several engineers, notably to Lurmann and to Lencauchez, who had pointed out the blast-furnace as a powerful gas-producer. Nevertheless, nowhere had any attempt been made to apply it to this purpose up to the end of 1894, when Thwaite proposed it to Mr. James Riley, of the Glasgom Iron & Steel Company. About the same time investigations were being made in Belgium and in Germany, independently of Thwaite's experiments, which were not generally known on the Continent. The industrial world, which up to that time had hardly favored the idea, had thus been gradually prepared to receive it. The gas-engine, long restricted to small sizes and dependent upon the use of an expensive fuel obtainable only in large centers, now began to make headway. At the Paris Exhibition of 1889 two engines of 100 h.p. were shown and excited much interest among engineers. One had four cylinders, and was made at the celebrated works of the Deutz Company, and the other was a single-cylinder engine, exhibited by two French designers, Messrs. Delamare-Deboutteville and Malandin. In the meanwhile the design of gas-producers had made important progress, completely freeing the new engine from its

Jan 1, 1907

NEW MEMBERS The following list comprises the names of those persons who became members during the period Nov. 9, 1918, to Dec. 10, 1918. ALBERT, EDWARD J 235 E. Upsal St., Philadelphia, Pa. BARRY, D. A Supt. of. Mines, The Big Five Min. Co., Idaho Springs, Colo. BATON, GEORGE S., Cons. Min. Engr., Baton & Elliott, 2412 First National Bank Bldg., Pittsburgh, Pa. BAXTER, HAROLD ALEXANDER, Met. Engr. & Operation Supt., Tacony Ordnance Corpn., Philadelphia, Pa. BENNETT, JOHN S., Chem. and Min. Engr Copiap6, Chile, South America. BOWDEN, MALCOLM, Min. Engr.; Efficiency Engr., Elm Orlu Min. Co., Butte, Mont. BROWN, HAROLD C 2d Lieut., A. S. A. P. BROWN, THOMAS ALBERT, Min. and Met. Engr.; Supt., The Royal Tiger Mines Co., Breckenridge, Summit Co., Colo. BROWN, WALTER S., Investigator, New Jersey Zinc Co. (of Pa.), Palmerton, Pa. BURDETTE, R.. S Capt., Ord. Dept., U. S. A. CALLANDER, IRA C., Asst. Supt., Gauley Mountain Coal Co., Jodie P. 0., Fayette Co., W. Va. COLLINS, J. W., Foundryman, The Aluminum Casting's Co., "L" Plant, Cleveland, Ohio,

Jan 1, 1919

By Kefton H. Teague

Olivine is a mineral containing a mixture of forsterite (Mg2SiO4) and fayalite (Fe2SiO4) in solid solution. The name olivine was first applied by Werner in 1790 (Hunter, 1941) because of the olive-green color of the mineral. Olivine is the principal component of the rock dunite, which itself is a member of the peridotite group of ultrabasic igneous rocks. European uses of the terms olivine and dunite are somewhat different than US usage. In commerce European usage defines dunite as containing 36 to 42% MgO, 36 to 39% SiO2, and loss on ignition of approximately 10%. The term olivine is used to designate a material containing approximately 85% forsterite, with a chemical composition of approximately 45 to 50% MgO, 40 to 43% Si02, 5 to 8% Fe2O3, and ignition loss of 1 to 2%. Uses The principal use of olivine is in various applications involving hot metal. Table I shows the best estimate available as to the amount of olivine consumed by various industries worldwide. In excess of 90% of world uses involve hot metal, with approximately 75% as a slag conditioner in the blast furnace production of pig iron. Approximately 15% of total olivine usage is as a special foundry sand in mold making for the brass, aluminum, magnesium, and manganese steel foundries (Schaller, 1957, 1958; Snyder, 1957; Anon., 1977). Olivine was first used as an industrial mineral in the early 1930s for a refractory material (Anon., 1970; Hunter, 1941). As a refractory raw material, olivine was first introduced in the United States as hand-cobbed, selected, shaped blocks of crude olivine. This use met with limited success. More recently, finely ground olivine blended with MgO and pressed into bricks, which are then fired, has found use in glass tank furnaces and open-hearth furnaces. Ramming or gunning mixes for basic furnace linings also utilize olivine. Olivine has been used in ladle linings with varied success. In Europe, substantial tonnages of olivine are utilized in refractory brick for night storage heaters (Anon., 1970). A limited amount of olivine has been used in the past as a fertilizer (magnesium source) and has been fused with rock phosphate to produce a magnesium phosphate as a plant food. The relatively high magnesia (MgO) content of olivine also attracted attention to it as a potential source of both magnesium compounds and as a source of metallic magnesium (Bengston, 1956; Hunter, 1941). The use of olivine as an additive in the blast furnace is relatively new, having been developed during the last decade. J.W. Currier (Private communication, 1978) describes the behavior of olivine in the blast furnace as follows: Olivine (Mg, Fe2, Si04) represents a unique lime-free source of magnesia and silica as a blast furnace charge component. Only recently has the magnesia-rich mineral been recognized as beneficial cleaner for blast furnace experiencing the problems associated with excessive alkali inputs and/or low coke stabilities. For some time it has been known that alkalis tend to recycle and accumulate in blast furnaces. In the high temperature region of volatilization the elemental alkalis formed attack the integrity of the graphite structure. This alkali attachment is enhanced when poor coke is used. Higher in the furnace stack volatile alkali cyanides condense and oxidize. This accumulation of alkalis tends to agglomerate the burden materials, producing scabs and scaffolds. These structures not only inhibit the downward movement of burden materials and the upward passage of wind, but also lead to erratic furnace performance

Jan 1, 1983

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

The first session of the Institute was held at the Smithsonian Institution, on Tuesday evening, February 22d. The members were welcomed to Washington and to the Smithsonian by Prof. Joseph Henry. President Holley responded to the cordial welcome of Professor Henry, and then read an introductory address on the subject of Technical Education. Following the discussion on President Holley's address the following persons, duly proposed and indorsed by the Council, were elected members and associates of the Institute : MEMBERS. Emile R. Abadie,. .. .. St. Louis, Mo. R. J. Anderson,.....Pittsburgh, Pa. Commander L. A. Beardslee,. .. Washington, D. O, Charles Bender,. .. .. New York City. Charming M. Bolton,. .. . Richmond, Va. Thomas E. Bowman,. .. . Silverton, Colorado. Calvin E. Brodhead,. .. . Bethlehem, Pa. M. L. Brosius,. .. .. . Lewistown, Pa. Harvey H. Brown,. .. .. Cleveland, Ohio. James A. Burden,.. .. . Troy, N. Y. J. P. Clemes,. .. .. . Sonora, Mexico. N. H. Cone,. .. .. . Nederland, Colorado. W. F. Durfee,.. .. . New York City. Robert Frazer, Jr.,. .. . Ashland, Pa, Joseph E. Galigher,.. .. . Bingham, Utah. William Golding,.. .. . Steel Works P. O, Pa. Samuel E. Griscom,.. .. . Pottsville, Pa. Gen. E. Burd Grubb,.. .. Beverly, N. J, Arthur R. Guerard,. .. .. Charleston, S. C. Edward Hart,.. .. .. Easton, Pa. Prof. Lewis M. Haupt,. .. . Philadelphia. E. S. Hawley,.....Buffalo, N. Y. John W. Hoffman,.. .. .. Philadelphia. Nelson P. Hulst,.. .. . Milwaukee, Wis. H. C. Humphrey,.. .. . Philadelphia. Ed. P. Jennings,.. .. .Ithaca, N. Y. B. F. Jones,......Pittsburgh, Pa.

By John C. Sawyer

A brief review is given to show that catastrophic oxidation of stainless steel in the presence of lead oxide is similar in many respects to catastrophic oxidation as caused by MoO3 and V2O5, Experimental data are presented to show that lead oxide accelerates the normal oxidation process of stainless steel by chemically altering the normally protective oxide film formed on the base metal. Data are given to show that similar reactions occur during oxidation of stainless steel in the presence of MOO3,and V2O5. THE mechanism by which pure metals oxidize at high temperatures has been the subject of intensive research for many years and much has been accomplished towards understanding the processes involved. The mechanisms by which alloys oxidize have also been investigated, but due partly to the fewer number of investigations and partly to the complexity of the oxide systems present, available knowledge is not as extensive as with pure metals. When oxidation processes are further complicated by atmospheres contaminated with sulfide, halide, or oxide vapors, the knowledge of fundamentals becomes meager or altogether lacking. Thus, it is not surprising to find that the catastrophic oxidation of stainless steels in metal oxide vapors of MOO, and V2O5 is not a well understood phenomenon despite the fact that a number of investigations have been undertaken. The literature in dealing with the subject of catastrophic oxidation is primarily concerned with the effects of MOO3 and V2O5, but does mention that other metal oxide vapors, one of which is lead oxide, appear to promote a similar type of accelerated oxidation. While this latter effect is virtually unknown, the deleterious effect of lead oxide is of considerable commercial importance, as it is believed to be one of the fundamental reasons for exhaust-valve failure in gasoline engines. For this reason studies have been in progress for many years attempting to better understand the mechanism involved. Modern exhaust-valve alloys"2containing 20 to 25 pct Cr plus nickel and/or manganese are in effect high-grade austenitic stainless steels exhibiting ex- cellent oxidation resistance in air at exhaust valve operating temperatures of 1100° to 1700°F; yet these same alloys are prone to corrode during engine service because of the conditions attending their operation. These conditions are such that the valves become coated with deposits of complex lead compounds mainly derived from gasoline additives of tetraethyllead, ethylene dibromide, and ethylene dichloride. Literature searches3-7 and discussions with various investigators show that considerable difference of opinion exists as to the nature of the lead-bearing deposits found on the surface of exhaust valves and the atmospheres to which they are subjected; yet, all seem to generally agree that corrosion, a gradual transformation of alloy to nonmetallic products of corrosion, is a consequence of the presence of lead compounds. This majority opinion seems to be substantiated by laboratory engine tests which show that corrosion does not occur to any appreciable extent when lead-free fuels are used. The first observations of catastrophic oxidation reported in the literature were probably made by pfeil,8 but it was Leslie and Fontana9 who undertook the first detailed study of the phenomenon. Their work was chiefly centered on the acceleration of oxidation which took place when stainless steels containing more than 3 pct Mo were heated in air with restricted circulation. These investigators reported that the presence of other oxides near the surface would further accelerate the rapid oxidation which occurred. While they recognized that the effect was attributable to the presence of molybdenum, it was Rathenau and Meijering" who emphasized the fact that the presence of molybdenum in the alloy was incidental to the presence of MOO3 vapor in the atmosphere surrounding the specimens. Evans,11 as well as Cunningham and Brasunas 12 studied similar

Jan 1, 1962

By Frank Firmstone

When in charge of the Glen don Iron Works, the importance of good methods of filling was forcibly brought to my attention, and it occurred to me that the first step toward the discovery of the best plans was the accumulation of exact information as to the distribution actually effected by various chargers; also, that something could be done in this direction by careful measurements in the furnace, to be afterwards recorded for comparison on drawings. The figures shown herewith have been prepared from such measurements, and nearly all of them refer to Glendon, where the fuel used was anthracite and the ore-mixture about threequarters of New Jersey magnetic ores and one-quarter of brown-ores from the vicinity of the works. Every occasion furnished by the blowing-in of furnaces was utilized, but the data accumulated rather slowly in this way; and, opportunity oEering to make special trials at no great expense, the figures from 2 to 7 were thus obtained. The trials were made by dumping a hopperful (6 barrows) of material at once into the furnace, and, when all the fuel of a round (12 barrows) had been put in, the profile of the upper surface was obtained by stretching a steel tape across the top on a diameter and at a known height. By measuring down from this with a graduated rod, the profile was easily obtained with sufficient accuracy, especial pains being taken to get correctly the crests of the ridges and the bottoms of the hollows, as many intermediate points being included as seemed necessary. This was repeated on another diameter when there was occasion. The same course was followed for the limestone and ore.

Jan 1, 1899

By Robert S. Moehlman

Is recent years, exploration and development by diamond drilling has become a popular attack on the problem of finding new ore shoots and developing extensions of known shoots. Diamond drilling has been used in recent years in extensive sampling of disseminated copper deposits, in preference to churn drilling. At the Harvard gold mine, near Jamestown, California, Philip R. Bradley, Jr., general superintendent, reports that: "The Harvard work was a singular example of the reliance that can be placed on diamond drilling in evaluating an ore body." Drilling at the Harvard mine will be discussed in a subsequent section of the paper. So popular has diamond drilling become, indeed, that many who have had slight experience with drilling are inclined to regard it as a cheap cure-all. This paper proposes to show some of the limitations on the application of drilling and some of the steps that should be followed in drilling programs to obtain reliable results. Cost oF Drilling Drilling has the advantage, over shaft sinking and drifting, of lower cost and greater speed. As compared with churn drilling, the advantage of bringing up a coherent sample instead of fine cuttings for a sample is obvious. Diamond drilling is generally more expensive, however, and more engineering effort is required in combining the average of core and sludge samples. Exploration of drift walls by hammer drills to a depth of less than 30 ft. is generally cheaper than diamond drilling, but beyond this depth the diamond drill is cheaper and more efficient. The principal factor in determining cost of drilling is the character of the ground drilled. Broken ground with many fissures is most expensive to drill. Hard ground is less of a problem with diamond drills than with ordinary machine drills. Hardness or softness affects only the speed of drilling. Caving, easily washed, sandy or clayey ground requires continual cementing and casing, which is the greatest cost problem. Thus, soft, incompetent ground is more costly to drill than hard, massive ground. Cost of drilling per foot in good to fair ground varies from less than $I per foot, achieved in some districts in Ontario, the Mother Lode, and Missouri, to $5 per foot in many western states. In bad drilling ground, costs may range from $5 to $15 or more per foot, thus approaching the cost of drifting. Other factors that increase the cost per foot are: I. Short total length of hole drilled, so that the cost of moving in crews and equipment must be spread over a relatively few feet. 2. Cost of drilling per foot increases with depth beyond about 500 ft.. as more time is consumed in pulling rods' 3. Cost of preparing drilling stations, getting air underground to stations? etc' 4. Inaccessibility and lack of water on the job make for higher costs.

Jan 1, 1946

By P. B. Knuckey, D. Littleford

The Kalengwa mine, situated in a remote area of Zambia in Central Africa, has presented some unique problems to the planners engaged in developing the deposit. This small, high grade copper deposit contains some 1,688,000 tons of ore at a grade of 9.3% contained copper. Of this 362,000 tons is classified as high grade ore at 27.2% Cu, the coarse fraction of which can be fed directly to converters; 733,000 is classed as intermediate grade ore averaging 6.3% Cu, and 593,000 tons classed as low grade ore containing 2.1% Cu. The geology of the deposit and the establishment of the mining operation is fully described. A concentrator is being built at Kalengwa to treat the high grade fine product, intermediate, and low grade ore, whilst the coarse high grade ore will be trucked to the Copperbelt smelters for direct smelting. Details of metallurgical processing are given. The decision to truck the coarse high grade ore to the smelters on the Copperbelt necessitated the construction of a new 200-mile road, the setting up of a fleet of heavy ore transport trucks and associated equipment. The remoteness of the area from established communication facilities on the Copperbelt necessitated the provision of radio communications between Kalengwa and the head office at Kalulushi, and the establishment of a regular mine air service. The paper also describes the training of an unsophisticated local population in the operation of heavy plant and machinery, the establishment of the township, and the provision of health services.

Jan 1, 1972

By M. J. Blackburn

The ordering reaction and its effect on dislocation awangements in alloys based on Mg3Cd has been studied by transmission electron microscopy. Ordering occurs by the growth of ordered domains until they impinge, thus producing an antiphase domain boundary (APB) network. In the disordered alloy, slip is confined to the basal plane while in the ordered condition slip occurs on the basal, prism, and pyramidal planes. Superdislocations have been identuied on these planes and their origin and expected spacings are discussed and compared with the observations. The APBs between the dislocation pairs have been resolved and have proved useful in the identification of superdislocations. Observed slip structures are related to the changes in mechanical properties produced by ordering. At high temperatures magnesium and cadmium form a continuous series of disordered hexagonal solid solutions. At lower temperatures three ordering reactions occur; two based on the compositions Mg3Cd and MgCd3 are transformations to DO19-type superlattices while alloys based on the composition MgCd transform to a B19 lattice. The ordering process in alloys near the composition Mg3Cd has been studied by several workers'-4 and it has been shown to be a first-order type transformation. The variation of mechanical properties with the degree of order and temperature have been reported in some detail by Stoloff and Davies.5 It was shown that the disordered alloy was stronger and less ductile than the ordered alloy, the differences being attributed to changes in the number of active slip planes and to the presence of short-range order in the disordered alloy. In this investigation the ordering reaction has been qualitatively followed by transmission electron microscopy. The effect of this ordering transformation on the dislocation arrangements in deformed specimens has been studied in some detail. EXPERIMENTAL Alloys were melted in a stainless-steel crucible under a flux and chill cast; both melting and casting were performed in an argon atmosphere. The ingots were hot-rolled and tensile specimens cut from the resultant strips. Some large-grained specimens were grown by the strain-anneal method. Heat treatment was carried out in inert atmosphere furnaces and in oil baths at the lower temperatures. Thin foils for transmission electron microscopy were produced by electropolishing in a cooled solution (temp = -40°C) containing 50 cu cm of nitric acid and 180 cu cm of methanol at a potential of 10 v. The ordering reaction was followed by transmission electron microscopy, X-ray, and electrical resistivity measurements but this paper will be concerned chiefly with the electron-microscopy results. Much of the work described in this paper was performed on an alloy containing 26.10 at. pct Cd although two of the micrographs are taken from work on a 25.55 at. pct Cd alloy. RESULTS i) The Quenched Solid Solution. Specimens which were quenched from above the critical temperature showed diffuse superlattice reflections. sark-field analysis on these reflections failed to reveal the presence of ordered domains and thus the superlattice reflections were assumed to arise from regions of short-range order. Quenching from temperatures of 400" to 450°C results in the formation of dislocation loops and helical dislocations. Such defects have been observed and analyzed in detail in several hexagonal metals6-' and as the crystallography and interactions of such loops appear similar in this alloy they will not be reported in detail. Fig. 1 shows a high density of loops

Jan 1, 1968

By H. H. Hausner, H. S. Kalish

IN recent years zirconium and beryllium have become of great interest because of their special properties. Zirconium is known for its remarkable ability to absorb the gases oxygen, nitrogen and hydrogen, has extensive use as a getter in electron tubes and has indeed become the primary metal in the manufacture of photoflash bulbs. Beryllium is of interest because it is light metal and as such could supplement aluminum and magnesium in light metal applications. The late development of zirconium ductile at room temperature produced by both the iodide and calcium reduction methods has stimulated frequent articles on this metal in the recent literature. Beryllium is so closely akin to zirconium crystall-ographically that some investigators are of the opinion that beryllium should be ductile at room temperature if it were pure enough. The crystallographic relationship of beryllium and zirconium, the interest created in Be-Zr alloys where the zirconium is believed to function as a remover of solid solution gas in beryllium and thus increase the ductility of the beryllium rich alloy, and the amenability of these metals to powder metallurgy methods stimulated this approach to an investigation of the system Be-Zr. Preliminary work showed that a zirconium compact melted when pressed in contact with a beryllium compact and sintered at 1250°C, without any apparent final bond between the two. A search of the literature revealed nothing pertinent about the Zr-Be system or about any zirconium - beryllium alloys. In 1936 Misch³ vaguely identified the compound ZrBe2 and reported that it has a deformed cubic structure. Two patents," , were issued to Mach-lett Laboratories in 1943 and in 1946 regarding the addition of small amounts of zirconium to beryllium in order to improve the ductility of beryllium so that it may better be used for X ray windows. In considering the alloy formation of beryllium with other metals Raynor thought it unlikely that zirconium would have any solid solubility in beryllium. From this indefinite information nothing could be ascertained about the possible use of Zr-Be alloys or the use of these metals intimately. A brief preliminary study of the system Zr-Be by powder metallurgy methods was undertaken to provide regions for more intense studies of Zr-Be alloys and as a guide to a formal phase diagram determination. The investigation described in the following pages was completed in less than three weeks. The usefulness of this rapid method to facilitate phase diagram studies and new alloy investigations will be shown. Materials and Procedure Zirconium powder was produced from crystal bar stock of high purity supplied by Foote Mineral Co. The crystal bar was converted to hydride at 730°C, crushed, and the hydride decomposed in purified argon at 850°C. 60 pct of the powder passed through a 325 mesh screen, 40 pct of the powder was —140 mesh, +325 mesh and the average particle size of the total was 8 to 12 microns. The beryllium powder was used as re-

Jan 1, 1951

By Harold S. Morgan

INTRODUCTION The Waste Isolation Pilot Plant (WIPP) is being developed in southeastern New Mexico by the United States Department of Energy as a research and development (R&D) facility to demonstrate the safe disposal in salt of radioactive wastes resulting from defense activities. As part of the WIPP R&D program, a series of in situ tests will be performed to determine the behavior of drifts and storage rooms in the creeping salt medium (Matalucci, et al. 1982). Data obtained in these tests will be used to evaluate and improve numerical models used to compute the structural response of these drifts and rooms. Stress has been proposed as one of the parameters to be measured in the tests, and borehole inclusion stressmeters have been included in the instrumentation package. Cages of this type provide an indirect measurement of stress change in that they actually monitor borehole displacements which are then related to changes in the in situ stress away from the borehole. The relationship between stress and displacement is highly dependent upon the constitutive behavior of the rock in which the gage is emplaced. This relationship is well understood for rocks with linear stress-strain behavior (Fossum, et al, 1976), but, for creeping rocks like salt, the relationship has yet to be determined. Thus, inclusion gage response in salt must be investigated fully before stress measurements from the WIPP in situ tests can be used for comparisons with computed stresses The calculations presented in this paper were performed as part of an investigation of inclusion stressmeter performance in salt. They focus on the strain gaged stressmeter (SGS) (Cook and Ames, 1979) and on a hypothetical solid cylindrical inclusion with variable stiffness Issues addressed include the effects of creep and the effects of gage stiffness on stressmeter output for various loading conditions. The

Jan 1, 1984

By W. S. Owen, T. Bell

The variation ox the M, temperature with nitrogen concentration has been determined experinzentally. The free-energy difference between martensite and the parent y Phase at the M, temperature,is computed for Fe-C and Fe-N alloys using recent solubility data fm the Fe-N system and new data for the variatim of the activity of the interstitial solute in the y phase with concentration. The "geometric model" is considered also, and the importance of Zener ordering is noted. It is shown that, although at any chosen concentration the M, temperature and the activity are significantly different in the two alloy systems, the free-energy duference is the same within the limits of experimental error, thus Providing further evidence of the very close similarity between the martensite transformations in Fe-C and Fe-N alloys. TO estimate the free-energy change accompanying the martensite transformation in binary interstitial alloys it is necessary to know the variation of the Ms temperature with interstitial solute concentration and some thermodynamic data. To date, only the Fe-C system has been discussed because this was the only system for which relevant experimental measurements had been made, but even in this case the data available are insufficient to permit the free-energy change to be calculated without the assumption of a thermodynamic model for the y and a solid solutions. The last comprehensive discussion of the topic was by Kaufman, Radcliffe, and Cohen in 1.960.' Since that time Ellis, Davidson, and Bodsworth2 have redeter mined the activity of carbon in y iron as a function of carbon content and Atkinson3 has measured the activity of nitrogen in Fe-N austenite. The M, temperature of Fe-N is reported in the present paper. Thus, it is now possible to assess the free-energy change accompanying the martensite transformation in Fe-N alloys on the same basis as that used to assess the change in Fe-C alloys. This comparison is of interest because it has been shown recently4 that the structure of the martensite formed in Fe-N alloys changes with nitrogen content in a manner exactly parallel to the changes in structure in the Fe-C series and that the strain associated with the distortion of the iron lattice in either the y or the a phase by a nitrogen atom is the same as that produced by a carbon atom. The work to be described tests whether or not this close similarity between the two systems extends to the thermodynamics of the martensitic transformations. THE Ms TEMPERATURES FOR Fe-N MARTENSITE Bose and Hawkes5 found the M, temperature of a eutectoid Fe-N alloy (2.35 wt pct N) to be 35°C. This single determination appears to be the only reported measurement of the M, temperature of an Fe-N alloy. In the present work a series of more than fifteen different specimens containing between 0 and 2.7 wt pct N were prepared by controlled nitriding of pure iron wire 0.010 in. diam. The iron was supplied by B.I.S.R.A. and was designated ACN2. The nitriding procedure, all aspects of which are critical, has been described in detail elsewhere.' Each specimen was quenched from the austenitizing temperature into brine at 20°C without removing the specimen from the ammonia-hydrogen atmosphere in which it was ni-trided. Alloys containing up to 0.7 wt pct N were fully martensitic. More concentrated alloys contained progressively more retained austenite. At 2.34 wt pct N the specimen was completely austenitic after quenching to 20°C. The M, temperature of specimens with M, temperature above 20°C (those containing less than 2.35 wt pct N) was determined by a thermal arrest technique. For the more concentrated alloys (2.35 to 2.70 wt pct N) the variation of electrical resistance with temperature down to -196°C was used. Unlike Fe-C alloys, Fe-N alloys cannot be reaus-tenitized in vacuum or in an inert atmosphere because excessive loss of nitrogen occurs, even in short times, at high temperatures. Consequently, the alloys were reaustenitized in the ammonia-hydrogen mixture corresponding to nitrogen equilibrium at the temperatures used. The specimens were quenched in a blast of cold hydrogen gas and the temperature, measured by a thermocouple welded to the 2.5-in.-long specimen, was recorded on a high-speed recorder. In the first experiments 0.002-in.-diam chromel-alumel wire thermocouples were used but it was found that these gave erroneous readings due to contamination by nitrogen pickup. Pt-Pt 13 pct Rh wires of 0.002 in. diam were found to be satisfactory. Further details of the experiments are available in the original thesis.7 The cooling rate was controlled between 400° and 4000°C per sec by adjusting the hydrogen pressure. At least three cooling curves were obtained for each composition. Each specimen was analyzed for nitrogen after quenching. To aid in the accurate location of the martensite arrest points a series of cooling curves of 0.010-in.-diam platinum wire were recorded and these, which did not contain an arrest, were used as comparison standards. Four specimens, each in the form of a 3-in. loop, were prepared from each of the four alloys containing more than 2.35 wt pct N. One specimen was used for nitrogen analysis, one for X-ray diffraction, and two for resistance measurements below 20°C. The latter specimens were quenched from 20°C into constant-temperature baths at selected lower temperatures.

Jan 1, 1968

By Christopher G. Atwater

The object of this paper is to describe and discuss the progress that has been made, up to the present date, in the development of the modern by-product coke-oven. There are few members of the Institute who have not heard more or less of the by-product oven-installation, and there are many whose acquaintance with it is intimate and practical. Since the general opinion on the subject has hardly become crystallized as yet, it is hoped that this paper will at least furnish matter for discussion. In order to obtain an idea of the present status of the industry in the principal iron-producing countries, the following table has been prepared : Table Showing Proportion of Coke Made in By-Product Ovens in Various Countries. United Kingdom (1898, Mr. George Beilby). Short Tons. Per Cent. Coal coked in by-product ovens,. .. 1,400,000 7.9 Coal coked in blast-furnaces with by-product recovery,.......2,240,000 12.7 Coal coked in non-by-product ovens,. . 14,000,000 79.4

Jan 1, 1903

By J. J. Beeson

The second part of the paper includes a detailed account of the processes of secondary-enrichment which have been effective in producing the disseminated ores. While both parts present new features, it is hoped that the discussion on secondary chalcopyrite and bornite may be of interest to those who are engaged in the study of secondary processes in other districts. The excellent work' Economic Geology of the Bingham Mining District, by J. M. Boutwell, was published in 1905. Since that time the extensive development work-surface cuts and underground drifting-of the Utah Copper Co. has made possible the collecting of samples for more detailed microscopic study. The writer has taken advantage of this fact and presents the following work, not as a criticism, but as a' continuation of the work which was begun by Mr. Boutwell. b. Acknowledgments.-The present study was undertaken at the suggestion of Dr. A. F. Rogers; to him, and to Prof. C. F. Tolman and Prof. S. W. Young, the writer wishes to express his thanks for criticism in the preparation of this paper. The writer also expresses his thanks to D. C. Jackling, Vice-President and Managing Director of the Utah Copper Co., for permission to publish this paper, and to William Spencer, D. W. Wadleigh, T. S. Carnahan, J. A. Caulfield, Percy Dayer, and Edward Norsefall, for the courtesies extended to him while a co-worker in the mines.

Jan 11, 1915

By A. Eilers

The use of the bag-house for filtering out fumes produced in certain metallurgical operations is not new in America. There are no patents in force at this time, to my knowledge, which might hinder such use. Up to about 25 years ago the bag-house was only employed in connection with either zinc-works, which produced the oxides, to be sold for paint, or as an auxiliary in extracting lead from high-grade oxidized ores and from galena-concentrates in the Missouri and neighboring lead-regions; this work being then done in the Scotch or American hearths and in very low slag-furnaces, in all of which was produced an excessive amount of oxides which were also finally sold as paints. The literature1 on the above is abundant in text-books and periodical publications. The first large bag-house to be used permanently in connection with lead blast-furnaces was erected, as far as I am aware, about 1887 at the Globe smelting Co.'s works at Denver, Colo., under the Lewis-Bartlett patents. The brick flue, running from the blast-furnaces to the bag-house, was only a few

Jan 1, 1913

By C. J. Rosa, W. C. Hagel

An attempt is made to determine the diffusion coefficients of oxygen ions in hypostoichiometric zirconium oxide. A phenomenological theory is developed for three-phase, unidirectional volume diffusion of a gaseous species from a planar source. Knowledge about oxygen diffusion in a and ß zirconium and experimentally measured rates of movements of interfaces permit the evaluation of oxygen ion diffusivi-ties in ZrO2-x. The results conform to the relationship: sq cm per sec, for the temperature range of 875" to 1050° C. DIFFUSION coefficients of oxygen ions in stoichio-metric oxides have been studied by many investigators. The obtained results not only supplement the knowledge about the lattice-defect structures of oxides and conduction mechanisms but also provide information of technological importance. Rate processes such as oxide sintering, high-temperature creep deformation, and oxidation of metals and their alloys are directly dependent on diffusion phenomena. Unfortunately, diffusion coefficients obtained from studies on stoichio-metric oxides cannot be treated without restraints when applied to oxidation kinetics, if precise evaluations of oxidation rates are desired. Oxides formed on metals are usually nonstoichiometric and exhibit nonuniform distribution of either cation or anion vacancies across their thicknesses. Debuigne and Lehr1 extended Danckwerts'2 mathematical analyses and furnished a semitheoretical treatment for evaluating oxygen diffusion coefficients in zirconium oxide in terms of weight gain measurements during oxidation of zirconium in the temperature range 400° to 850°C. Their calculations are based on theoretical partitioning3 of the total amount of oxygen between a zirconium and its oxide phase. An inherent discrepancy appears to continue throughout their calculations. The amount of oxygen confined to the oxide phase should be corrected by multiplying the calculated oxide thickness by the inverse of Pilling-Bedworth ratio, if expansion of zirconium dioxide is taken into account. The purpose of the present investigation is to provide a new semitheoretical treatment for evaluating diffusion coefficients of moving species in hypostoichiometric oxide. The analyses are relevant to unidirectional volume diffusion. Although the presented method is quite general, its applicability will be discussed in terms of kinetic measurements from oxidation of zirconium at temperatures above the a/ß transition, for reasons stated in the later part of this paper. EXPERIMENTAL Pure, 99.93 wt pct, zirconium samples of approximately 2 by 1 by 0.35 cm were exposed to oxygen for various times at four temperature levels: 875°, 950°, 1000°, and 1050°C. High-purity, better than 99.9 vol pct oxygen was passed through a cold trap and columns containing anhydrous CaSO4 to remove residual water vapor. Before exposing to oxygen at a pressure of 500 Torr, specimens were subjected to wet abrasion on 200- through 600-grit Sic papers and polished with 1—p diamond dust. Prior to oxidizing, all zirconium samples were vacuum-annealed at 10-6 mm Hg for about 15 min at the test temperature. The temperature variation across the uniform heat zone was ±2°C from the preset value. Final polishing, for phase thicknesses measurements, was performed by using 8- and 1-p diamond dust and followed by vibrator polishing with 0.05-µ ? Al2O3 solution. Measurements of phase thicknesses were made by projection on a metallographic viewing screen. Conventional powder X-ray analyses for the oxide were employed. RESULTS Fig. 1 is an example of the cross section of oxidized zirconium. Designations of phases given below this figure are the same as those used in the three-phase diffusion system represented by Fig. 5 in the following section. Zirconium oxidized for longer exposure times showed two types of oxides: white oxide at the surface and an underlaying layer of gray oxide. X-ray powder patterns of these oxides at room tern-

Jan 1, 1969

By C. S. Barrett, O. R. Trautz

PREVIOUS investigations have shown that lithium is body-centered cubic from near its melting point to the temperature of liquid air1,2,3 Nevertheless there was an incentive to search again for a transformation at low temperatures: C. Zener4,5 has remarked that the low value of the elastic modulus (11 - C12)/2 of body-centered cubic metals and alloys implies a rapid increase in free energy with decreasing temperature, which would favor the occurrence of a transformation; also the shear movement to which this modulus applies is one that can transform a body-centered cubic structure into a slightly distorted face-centered cubic structure. It was confirmed that lithium does not transform spontaneously at liquid nitrogen temperature, but it was found that a transformation can be induced at this temperature by cold working the metal,6 and at slightly lower temperatures a different transformation occurs spontaneously. Transformations were also found in solid solutions of magnesium in lithium. THE NATURE OF THE TRANSFORMATIONS Before presenting a detailed treatment of the technique used and the specific data obtained, it would be well to give a brief survey of the general characteristics of the transformations. A new crystal structure begins to form spontaneously in a specimen when it is cooled below a critical temperature. In lithium the structure appears to be close-packed hexagonal; in the Li-Mg alloys most of the diffraction lines (but not all) are near those for hexagonal lithium. The transformation proceeds as the temperature is lowered and soon stops if the temperature is held constant or raised. The course of the transformation on cooling is indicated by the curve at the lower left of Fig I. This curve is drawn in stepped fashion because the transformation goes by discrete steps with audible clicks. Because of the similarity to the decomposition of austenite into martensite in steels, it seems appropriate to designate the beginning of the spontaneous transformation on cooling as the Ms point. On heating to room temperature after the low temperature treatment only the usual BCC structure is found. On heating, the low temperature modification begins to disappear at a temperature which will be designated as Ac. The transformation on heating is halted when the rise in temperature is halted. The temperature must be raised 40 to 50°C above Ac before the reversion is complete-an interval which is sensitive to the rate of heating and to the time of holding at temperatures above Ac. This behavior on heating thus has similarities also to the formation of martensite in the cooling of steels.

Jan 1, 1948

By S. A. Braley

DRAINAGE water from coal mines is probably the most serious water pollution problem today, varying in importance according to location of the mines and geological structure. Drainage may be either acid or alkaline in character. Acid discharge, the most severely detrimental to a stream, is caused by natural oxidation of the sulfuritic material (FeS2) in the strata associated with the coal seam. Since the acid is the result of a natural reaction the acid water differs because it does not cease with abandonment of the mining operations. There is no known economical method of neutralizing acid mine water or any practical method to prevent oxidation of exposed pyrite. Since production of acid from a mine does not stop when mining stops, the total quantity produced depends entirely upon the excavated areas. The increasing volume of acid water in manv mines has greatly increased operating costs. Pumping is expensive and acid mine waters are destructive of all equipment, especially metals in pumps and piping, and necessitate the use of corrosion-resistant materials. Discharge of the acid mine drainage into streams neutralizes their normal alkalinity, causes them to become acid, and produces an environment unfavorable for aquatic life and unsuited for industrial or domestic use without costly treatment. Mine drainages vary in percentage composition over wide limits, although the usual dissolved substances are ferrous and ferric iron, aluminum, calcium and magnesium sulfates, and lesser amounts of sodium, potassium and manganese sulfates and chlorides. Some alkaline discharges may contain heavy concentrations of iron as iron bicarbonate. These waters may produce iron hydroxide deposits in the receiving stream but do not cause it to become acid. In the extensive literature on acid mine water there appears to be a great deal of confusion about the importance of various components and the methods for their determination. In many instances faulty conclusions have been drawn from use of unsuitable methods of analysis. It is desirable that the factors and terms used in evaluation of analyses of mine waters should be so clearly defined that any interested person could properly appraise any analytical report. Some analysts report complete chemical analyses of mine waters and neglect to record drainage volumes. Others report only a minimum of analytical data after taking no precautions to preserve the original composition of the water during the time elapsing between collection and analysis. Some use methods of analysis intended for so-called pure waters of the potable and boiler water classes. These methods are not applicable to highly buffered waters such as mine water. Probably the most common criteria for evaluation are pH, free acidity, or acidity or alkalinity to methyl orange or methyl red, total acidity or acidity to hot phenol-phthalein, and the sulfate content. If these determinations are made on carelessly collected samples after a few days to weeks standing in warm rooms, they do not in any way represent the character of the water flowing from the mines. It is hoped that a brief discussion of the fundamental value of some of these factors may lead to a bettqr understanding of the need for more careful evaluation of mine water discharges. The term pH is one used by chemists to express relative acidity or alkalinity in terms of concentration of effective hydrogen ion in a solution. It is defined as the negative logarithm of the hydrogen ion concentration or activity in equivalents per liter. pH = logarithm A neutral solution, which is one containing the same number of hydrogen and hydroxyl ions, has a pH of 7. As the hydrogen ions increase and the solution becomes more acid, the pH decreases toward zero; and as the hydroxyl ions increase and the solution becomes more alkaline, the pH approaches 14. When dissolved in water to a dilute solution acids like sulfuric and hydrochloric, commonly known as strong acids, ionize completely, and the pH or hydrogen ion concentration varies with molar concentration of the dissolved acid. However, in high concentrations of such acids, the pH or hydrogen ion concentration is less than the acid concentration because the acid does not completely ionize. In only very dilute solutions does the pH represent the total amount of acid that can be neutralized by an alkali. All ionization reactions are equilibrium reactions. If other chemicals are added to the solution of an acid and the added chemical produces an ion that is the same as one of the ions of the acid, the degree of ionization of the acid is altered and the pH changes to some value that represents the active hydrogen ion of the new solution. Thus if iron sulfate is added to a solution of sulfuric acid the pH increases, since the common sulfate ion suppresses the degree of ionization of the sulfuric acid and decreases the effective hydrogen ion. However, the total acidity of the solution is increased. There are two salts composed of iron and sulfate— ferrous and ferric sulfate. In these salts there is no hydrogen ion that can ionize to give an acid solution, but when they are dissolved in water, the pH is less than 7 and the solution becomes acid. This is caused by a reaction known as hydrolysis and is represented by the equations FeSO4 + 2H2O ? Fe(OH)2 + 2H + SO,: or Fe,(SO,)3 + 6H2O ? 2Fe(OH)3 + 6H+ + 3504 A solution with a total acidity of 5000 ppm according to the first equation will have a pH of 4.40 but one with an acidity of 75 ppm, according to the sec-

Jan 1, 1958

By Matsubara, A.

THE problem of the equilibrium between iron, carbon, and oxygen was first carefully investigated by E. Baur and A. Glaessner,1 who determined the equilibrium conditions of the two reactions Fe304 + CO ? 3FeO + C02 (1) FeO + CO ? Fe + C02 (2) within the range of temperature of 350 to 900° C. The next series of investigations was made by R. Schenck and his co-workers,2 who sought to check the results of Baur and Glaessner's work within the range of 550° to 700° C. and to elucidate the conditions of formation of iron carbide. The equilibrium conditions at the higher temperatures, however, are generally understood to be much more complicated, owing chiefly to the formation of solid solutions between iron, its oxides, and carbide; nevertheless their determination is of much more practical importance than those at the lower temperatures. It is well known that each of the reactions is reversible; equilibrium is established when the partial pressure of oxygen in the gaseous phase has become equal to the dissociation pressure of magnetic oxide in equation 1 and that of ferrous oxide in equation 2. These equilibria are subsequently designated by "the Fe304-FeO equilibrium" and "the FeO-Fe equilibrium," respectively. As the Fe304-FeO equilibrium has three phases with three components, it must be bivariant. But the reaction involves no pressure change in the gaseous phase, hence the final composition of the latter is practically unaffected by pressure. To know, the equilibrium conditions, the compositions of the gaseous phase at different temperatures must be determined. At the higher temperature, however, iron and its oxides dissolve one another in various proportions forming solid solutions; in many cases the content of oxygen in the solid phase becomes a new independent variable.

Jan 2, 1921