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By John C. Bilello

The brittle fracture behavior of cold-worked sintered tungsten was studied over the temperature range 4.2° to 298°K using a high-sensitivity strain measuring system and electronfractography. Similar observations were made on a swaged electron beam zone-refined monocrystal. In sintered tungsten irreversible plastic deformation was observed during cyclic load-unload tests at stress levels well below the fracture stress for all temperatures, but general microyielding could be detected only down to 202°K. For the zone-refined samples macroyielding occurred at all test temperatures with evidence for twinning below -202°K. The fracture stress of the sintered tmgsten was virtually independent of temperature, while the zone-refined crystal showed a 2.3 times increase over the same temperature range. Electronfractography confirmed the presence of numerous rod-shaped and spherical submicroscopic voids which ranged in diameter from 1400 to 4300A in the sintered tungsten; no voids could be found in the zone-refined tungsten. Contrast effects observed on the replicas in the vicinity of certain voids indicated that plastic deformation could be induced by the local stress concentration. It has been suggested that the presence of these voids may be responsible for the low-temperature brittle failure of sintered tungsten. Based m this suggestim und on the evidence obtained here, a dislocatim model is presented to account for the brittle behavior of sintered tungsten. In this model slip, which is induced by the local high stress concentration in the region at the edge of a favorably oriented void, could cause the void to grow to a microcrack of critical size. STUDIES of brittle fracture in bcc metals have led to the well-known experimental relationships between grain size, yield stress, fracture stress, and temperature which have formed the basis for the various dislocation pile-up1-3 or interaction4'= models for slip-induced microcrack nucleation. While microcracks can be nucleated by deformation twins,6,7 there has been no direct evidence furnished by transmission electron microscopy to support conclusively either the Zener pile-up or Cottrell dislocation reaction models for producing micro-cracks in all "brittle" materials. In addition to the "inverse" grain size relationship for yield and fracture stresses the cottrel14 theory predicts that the fracture stress below the transition temperature should behave in a fashion similar to that of the yield stress above this temperature. Such behavior has been verified for several bcc metals.8-10 With reference to both grain size effects and the tem- perature dependence of the fracture stress below the transition temperature, the behavior of sintered tungsten appears anomalous. Early work by Bechtold and Shewrnon 11 showed no apparent temperature dependence of the fracture stress below the ductile-brittle transition temperature (DBTT). They attributed this result to the intergranular nature of the fractures observed. More recent work by Wronski and Four-deux12'13 on considerably purer material did not show any systematic relationship between the fracture stress and temperature below DBTT. The dependence of flow and fracture stresses on grain size is also not clearly established for sintered tungsten. Koo, for example, has shown that the DBTT for sintered tungsten depended chiefly on the annealing temperature and was relatively insensitive to the actual grain size achieved. Using electrofractography and transmission electron microscopy, Wronski and Fourdeuxl3 showed that numerous spherical and rod-shaped submicroscopic voids could be found in sintered tungsten but not in melted tungsten of nominally the same purity. They suggested that these voids could be responsible for the temperature insensitivity of the fracture stress below the DBTT. In the present work the temperature dependence of the fracture stress for high-purity commercially sintered tungsten has been determined. The presence of submicroscopic voids in sintered materials was confirmed, and these were studied in detail to examine the role they could play in nucleating brittle fracture. A dislocation model is suggested which could cause an inherent spherical void to lengthen into a Griffith crack of critical size. EXPERIMENTAL PROCEDURE Commercially sintered tungsten rod was obtained in the as-swaged condition from Sylvania. A zone-refined crystal was obtained from the same source. This crystal was grown by giving three zone passes (at 25.4 cm per hr) to a sintered rod of high-purity tungsten. The rod axis prior to cold working was -15 deg from the [110] direction. Originally the zone-refined rod was -6 mm in diam; it was reduced to -3 mm by eight swaging passes, at high temperatures, with each step having about the same reduction of area. The final swaging step gave a 7.5 pct reduction of area at 1050°C. All swaging operations were performed in a hydrogen atmosphere. For the sintered rod a similar working schedule was employed. Metal-lographic examination of the sintered material revealed that the cold-worked structure had an apparent grain diameter of -25 u transverse to the swaging direction (obtained by the intercept method). In the longitudinal direction cold-worked grains were approximately 1.5 to 2 times their diameter. No distinct fiber structure could be observed optically for the zone-refined rod. The cold-worked structure in the

Jan 1, 1969

By John A. Hansuld

Molybdenum presents a series of baffling geo- chemical puzzles. It can exist in six different valence states, possessing three different coordination numbers. As a result, it combines with other elements to form a wide variety of negatively and positively charged ions and complexes whose exact chemical nature are relatively unknown. Its rather complex chemistry might be described as "ambidextrous, bi-sexual and polygamous". It is little wonder then that the geochemistry of molybdenum is relatively unknown, and compared to most common metals its geochemical behavior is somewhat unique. The behavior of a particular element or metal, such as molybdenum, in a given dispersion media is largely controlled by the stability relations among its various oxidation products. Recognition of these products and an understanding of their stability relations is therefore a prerequisite to a proper understanding of its observed behavior. Because most secondary dispersion media represent aqueous chemical systems, stability relations are best expressed as functions of Eh and pH.

Jan 12, 1966

By John Birkinbine

FOR two years past the Warwick Furnace, at Pottstown, Pa., has attracted attention by the remarkable work done in it, and a statement giving details of its operation and the unexpectedly short blast of 1880 will be acceptable to every member who studies blast-furnace practice. There are so many interesting features in con¬nection with this blast, and so much to be learned from investigating it, that the results of a thorough examination are offered to the Institute sans theories. In collecting the information, the courtesy of the various officers of the Warwick Iron Company was of material advantage, every facility for investigation being extended and an inspection of records being kindly permitted. In the following description these authoritative data are given in full where practicable, without making the paper too prolix, and the

Jan 1, 1881

By P. Somasundaran, D. W. Fuerstenau

This article presents the results of an analysis of grinding of 1:1 mixtures of 4x8-mesh quartz and limestone in laboratory ball and rod mills. From these experiments, the amount of energy consumed in grinding each component of the mixture was determined. In the ball mill, limestone consumes slightly more energy than quartz in the initial stages of grinding, but as the grinding proceeds quartz begins to consume a slightly greater fraction of the energy. The postulate that the fraction of energy consumed by any material in a ball mill is proportional to its volume fraction has been shown to be approximately true. On the other hand, in a rod mill energy consumption by quartz and limestone is equal only in the initial stages of grinding, with energy consumption by quartz greatly exceeding that by limestone as rod milling proceeds. Preferential energy consumption in tumbling mills has been discussed in a number of papers. For example, from an analysis of the kinetics of comminu- tion in ball mills, Arbiter and Bhrany' obtained rate equations based on the postulate that only coarse particles are ground, indicating that fine particles are protected from the action of the balls by coarser particles. In rod mills this protective action is much more pronounced than in ball mills. Recent studies on the rod milling of limestone-quartz mixtures have shown that this protective action causes the mineral with the lowest grindability (quartz in this instance) to consume the greater fraction of energy. 2 However, in the ball milling of mixtures it has been postulated that the consumption of energy by one of the constituents is determined by its volume fraction within the mill. 3 Possibly this hypothesis may be a simplification of the ball milling of mixtures since the protective action suggested by Arbiter and Bhrany may result in some preferential energy consumption by one of the constituents of a mixture. The objective of this study has been to determine preferential energy consumption in laboratory ball and rod mills by analyzing size distributions of each material in the products obtained from grinding 1:l mixtures of quartz and limestone. MATERIALS AND METHOD The procedure for carrying out the tests on wet grinding quartz-limestone mixtures has already been described.'r3 In the present investigation, 1:l mix-

Jan 1, 1963

By J. Leslie Goodier

The International Law of the Continental Shelf, so far ratified by 35 nations, extends the national boundary of any coastal nation to the edge of the continental shelf, this normally being at a continuous water depth of 200 m. The Law further extends this boundary to include the floor of the deep ocean to any depth that can be mined by advanced mining technology. In effect, proof of mining can constitute proof of ownership of the subaqueous land and the minerals on or below the sea floor. Irrespective of the fact that present technology is too limited to permit mineral exploitation in the high seas-and the law regarding the right to mine appears hazy-the U. S. Treasury Department's Bureau of Customs, has a ruling that would further deter mining operations on the high seas. This law contends that minerals mined on the continental shelf of the United States are actually mined within the continental United States and are free of tariff, but mined products or other articles obtained from the ocean or the sea floor beyond the continental shelf, if brought into this nation, must be considered as imported and are subject to such customs duties as are applicable under the tariff schedules of the United States.

Jan 7, 1968

By Edward Wisser

The environment of an ore body is taken to mean not only its physical surroundings but every factor, passive or active, that conditioned the ore shoot, saving only the original composition of the solutions that formed the shoot. Collection of data related to the shape and characteristics of veins should be followed by correlation of the data and the formulation of generalizations regarding ore formation. The nature of the criteria used in arriving at these generalizations is discussed. Certain of the criteria, when used with an understanding of their underlying causes, become "ore-guides." In the course of his study the geologist must not confine himself to the immediate surroundings of the veins, but should attempt to work out the geologic history of events culminating in the crucial epoch for any mining district, the period of mineralization. The work may involve study of features far removed from the veins and related to them only indirectly. It commonly means thorough study of the geology of the entire region surrounding the ore deposits. The following question has been suggested for discussion: "Are there any criteria by which one can determine when mining operations have reached the roots of an ore deposit?" The question deals less with the roots of a particular ore body than with the lower limit of the vertical range within which ore bodies may be expected. It concerns a critical line upon the longitudinal vertical projection of a vein.† Below this line it is useless to look for ore shoots; above the line exploration below the bottoms of individual ore shoots may be justified. Can we learn to determine the position of such a line? In some multivein districts the line for any given vein may be approximated by simple interpolation or extrapolation. Where this is possiblc the bottoms of the lowest ore shoots in the various veins are points on an imaginary, gently rolling surface. The trace of this surface upon the vein is our critical line for that vein. The imaginary surface rolls so gently that it may be projected from two or more known veins to an unexplored vein near by. Here is a criterion for the bottoming of ore that has nothing to do with changes in the appearance of the vein in question; it rests solely on the depth at which the ore bottomed in adjacent veins. The method is not applicable in districts only slightly explored in depth, nor where the lower limit of the ore-bearing horizons

Jan 1, 1941

By Gerald A. Munson, Fremont F. Clarke

DURING recent years the use of lithium has expanded greatly in industrial, chemical, and metallurgical fields, while at the same time modernized methods of mining and refining lithium have increased production. Technical literature includes many papers describing the geology and mineralogy of lithium deposits. Mining and beneficiating problems, however, have not been thoroughly described. Published reports have failed to emphasize that one of the chief reasons lithium minerals were not extensively mined until recently is the difficulty of beneficiation. Four lithium minerals of pegmatites and the lithium-sodium-phosphate byproduct from the brines at Searles Lake, Calif., have been sources of lithium. Among the pegmatite minerals, only spodu-mene and petaline are known to occur in deposits large enough to support large tonnage operations. Spodumene, a lithium-aluminum-silicate, is the principal lithium mineral mined in the U. S. Lithium Corp. of America, during its rapid development and growth, has successfully employed three different methods of concentration: 1) hand sorting, 2) Heavy Media separation, and 3) froth flotation. Each method, though economic in its sphere, is becoming outdated as extractive techniques improve. The most recent development has taken place at Lithium Corp.'s new operation in North Carolina, where the extractive process yields lithium compounds directly from mined rock without an intervening concentrating step. Until 1954 Lithium Corp. mined only in the southern part of the Black Hills of South Dakota, where the various types of lithium-bearing pegmatite could be used to develop untried processes of beneficiation. Concentrates from these operations are shipped to the corporation's chemical plant in St. Louis Park, Minn., where actual extraction of lithium and production of commercial compounds takes place. Nature of Deposits The geology of the southern Black Hills pegmatite deposits is admirably presented by a U. S. Geological Survey publication.' Only the factors pertinent to exploitation need be mentioned here. Lithium Corp. has been interested primarily in three deposits, the Edison, the Mateen, and the Longview-Beecher No. 2. The history of these deposits dates back to the mining boom of 1880 to 1900 in the Black Hills, when most of the deposits were prospected for tin by the ill-fated Harney Peak Tin Mining Co. The three deposits described here, however, lay idle and unwanted until Lithium Corp. opened the Edison mine in 1943 and the Mateen and Longview-Beecher No. 2 in 1951. Edison Deposit: The Edison deposit is about a mile southeast of Keystone, S. D., on the northeastern flank of the Harney Peak uplift. The deposit consists of no less than four and probably at least six separate pegmatites that coalesce in a central mass from which the individual pegmatites finger outward and downward in complexly folded schist and gneiss beds of the country rock.

Jan 1, 1956

By Carolyn Barnes

The Offshore Technology Conference, the world's largest technical conference and exhibition on the development of offshore resources and protection of the ocean environment, is sponsored annually in Houston, Texas, by 12 international engineering and scientific societies. This year's OTC, the seventh, will be held May 5-8 at the Astrodomain, and will be the largest in its history. The technical program for the first meeting in 1969 consisted of 100 papers, an exhibit display of 380 booths, and an attendance of 4300. This year. 280 technical papers are to be presented, and more than 2800 exhibit booths, representing some 1200 companies and nine countries, will be on display for an anticipated audience of 40,000.

Jan 4, 1975

JoHN W. BELL, Montreal, Quebec, Canada (communication to the Secretary*).-Mr. Taggart's reply illuminates a puzzling element in his original paper. Unconsciously, he has allowed practical considerations to influence some of his conclusions. In certain cases, he accepts the direct conclusions indicated by his Stadler efficiencies, and these are proved wrong by both the Rittinger and practical method for estimating efficiency. In other cases, a direct conclusion based on his Stadler figures would be so unsatisfactory to him, that he is. compelled to argue how he could have obtained satisfactory results if lie had crone something that

Jan 10, 1917

By T. F. Witherbee

IN a paper read at the Lake Superior meeting, August, 1880, an account was given of the successful use of Rendrock and Monaky powder upon a scaffoldn and salamander in the furnace. On April 5th, 1881, the same trouble called for like treatment, which, though not so immediately. successful, was on the whole more instructive than the first trial, and points, I trust, to a reasonably sure remedy for all such difficulties. Up to December 4th, 1880, foundry and mill iron were made from Old Bed and New Bed magnetite, and Kearneyy red hematite, when a return was made to Bessemer iron, from an inferior quality of New Bed ore as compared with that used during first blast. January 18th, 1881, New Bed, Chateangay, and East-shaft, a newly-opened Bessemer deposit of Messrs. Witherbee, Sherman & Co., were first used, and continued up to February 13th, on a fuel charge of 80 per cent. anthracite and 20 per cent. coke, the product on the three ores being about 10 tons more per day than on New Bed alone. From this time until March 11th all coal was used, and New Bed, Chateangay, and East-shaft ores, up to February 22d, and from that date Chateangay and New Bed, the product falling off 9 6/10 tons per day as a result of not using coke. It is fair, however, to state that the furnace was not in good condition during' this period, being over-burdened, and the New Bed ore was, temporarily, uncommonly poor, for reasons of no particular interest here.. It required to properly flux it at least 140 per cent. of limestone; and 101 per cent was actually used. March 11th, all Chateangay ore and 80

Jan 1, 1882

Jan 1, 1969

By George W. King

The yield strength of a dispersion-hardened W-3.8 vol pct Tho,alloy, in both the recovered and recrys-tallized condition, was investigated and cornpared with that ofrecrystallized pure tungsten over the temperature range of 325" to 2400°C. It is deduced that the Orowan mechanism is obeyed in the recrystallized alloy. In the recovered alloy, a further enhancement of the yield strength results from the retained substructure which is stable up to temperatures in excess of 2700°C. Temperature and strain rate cycling tests were also performed, and the apparent activation energy for the deformation process was derived. This activation energy, - 3 ev, for the recovered and also the recrystallized alloy was about the same as that for re crystallized pure tungsten. However, the activation volume of the recovered alloy, -10-2 cu cm, was about an order of magnitude lower than that of the recrystallized alloy or pure tungsten. This fact accounts for an enhancement oj- the temperature dependence of the yield stress of the recovered alloy. A dislocation velocity exponent of about 4 to 13 was deduced frorn the strain rate cycling tests , which is in good agreement with values reported for tungsten single crystals. VARIOUS theories have been developed to explain the enhanced yield strength of a metal containing a dispersed second phase of small hard particles. These theories are thoroughly reviewed by Kelly and Nicholson.' The theoretical models can be separated into two types. The first type assumes direct interactions between moving dislocations and dispersoids. One of the most widely investigated models for this mechanism is the bowing out of dislocations between the dis-persoids and their subsequent pinching off in order to bypass the obstacles. This is the well-known Orowan mechanism.' The second type is an indirect effect of the dispersion because of its ability to stabilize to high temperatures the substructure introduced by cold working. In this instance, the increment in the yield strength is expected to be inversely proportional to the square root of the subgrain diameter. In the present work, a quantitative study was made of the strengthening effect caused by a thoria dispersion in a recrystallized W-3.8 vol pct Thoz alloy over the temperature range 325" to 2400°C. The results are compared with the increment predicted for the Orowan mechanism based on the calculations by ~shb~.~ In addition, the alloy was tested in the recovered state so that any additional strengthening resulting from the substructure produced during fabrication could be measured. The respective contributions can be separated in this manner, provided that the particle size distribution of the dispersion remains the same in both the work-hardened and the recrystallized state. Particle size distribution measurements showed that this condition was met in the present work. I) EXPERIMENTAL PROCEDURES A) Material Production and Fabrication. The alloy investigated is essentially the same as that reported much earlier by ~effries,~ who also found the strength of tungsten to be improved by the thoria dispersion. The procedure for producing the alloy consisted of mechanically blending a thorium nitrate solution in proper concentration with tungsten oxide (WO3) powder, followed by hydrogen reduction to metal powder. After reduction, the dispersed second phase is present as thoria (Thoz). The pure tungsten powder used for comparison was produced in the same manner except that the thoria doping step was omitted. The powders were consolidated by cold pressing and self-resistance sintering in hydrogen. The resulting ingot had a cross section about 0.6 sq in. and a density about 93 pct of theoretical. The ingot was swaged to 0.174-in.-diam rod at temperatures varying from 1650°C initially to -1200°C near final rod sizes. Two intermediate recrystallization anneals were employed during fabrication. Analysis of the swaged rods is reported in Table I. B) Electron Microscopy Techniques. Carbon extraction rrPxcas prepared by a technique reported by ~00' were used to quantitatively evaluate the thoria particle size and distribution. Electron nlicrographs of extraction replicas were taken at 20,000 times but were then enlarged two to three times in printing. The areas photographed were randomly selected. A Zeiss Particle Size Analyzer (Model TGZ3) was used to count and measure the sizes of all particles present on the print. About three thousand particles were counted in determining a distribution curve. Electron transmission microscopy was used to determine the effect of annealing on the substructures of the materials. Thin foils were produced by a two-stage thinning process. The rods were first ground on emery paper to ribbons about 10 mils thick and then a jet of 5 pct KOH was used to electrolytically reduce a portion of the cross section of the ribbon. Final perforation was achieved by immersing the specimen in a 5 pct KOH solution and electrolytically polishing at a current density of about 0.3 amp cm-'. The foils were examined with a Hitachi HU-11A electron microscope. C) Tensile Testing. Tensile testing was performed in an Instron Testing Machine equipped with a radiation-type vacuum furnace which operates at about 1O"S torr at temperatures as high as 2400 °C. The same furnace was used for annealing the tensile specimens.

Jan 1, 1970

By M. H. Cullender

The performance characteristics 01 gas wells producing from formations which fail to stabilize within a relatively short period of time are obscured by the interrelation of the coefficient (C) and the slope "n" of the conventional back-pressure curve q = C(P2 f- p2s)n An empirical method is presented whereby the characteristic or true slope (11) of the back-pressure curve may be determined for a particular gas well. For those gas wells which do not stabilize within a relatively short period of time, the coefficient (C) is considered as a variable with respect to time and as a constant only with respect to a specific time. Thus, the back-presrure performance of such a well is presented as a series of parallel curve5, each curve representing the performance of the well at the end of a given time interval. Through use of the method presented, a simple presture gradient is developed and maintained within the drainage area around a producing gas well during the test period in order that the variation of the coefficient (C) with respect to time does not obscure the true value of the lope. INTRODUCTION The back-pressure method of testing gas wells as set forth by Schellhardt and Rawlins1 is dependent upon the requirement that a series of flow rates and corresponding pressure data be obtained under stabilized conditions. These data arc then plotted on logarithmic coordinates of flow rate (Q) vs difference in squared pressures (P2f — P2s) in order to determine the constants (C) and (n) for Equation 1. With respect to this method of presenting the performance characteristics of a gas well, it should be pointed out that although Equation 1 is an empirical relationship, the form of the equation was justified to a considerable extent by an independent development by Muskat and Botset.2 This development was theoretical in nature; however, certain assumptions with respect to the type of flow existing (viscous vs non-viscous) were madc which may or may not be correct. As the use of the method presented by Schellhardt and Rawlins spread through the industry, it became evident that the method of testing was applicable for those wells which approached stabilized prbducing conditions within a relatively short period of time. Performance characteristics could not be determined by this method, however, for wells which approached stabilized protlucing conditions slowly over a considerable period of time. This characteristic of "slow stabilization" has generally been associated with gas wells producing frorn reservoirs of low permeability. As the demand for natural gas continued to grow through the years, a great number of wells were completed in reservoirs of low permeability which exhibited "slow stabiliz:~tion" characteristics. Consequently, the problem of determining the true performancc characteristics of these wells became more apparent. It is with this problem in mind that the isochronal performance method of determining the flow characteristics of gas wells is presented.

Jan 1, 1956

By T. V. Falkie, D. R. Mitchell

Many operational problems in mine haulage cannot be solved economically by conventional analytic or trial and error methods. However, a method of probabilistic simulation, which is based on the fundamental assumption that many of the variables governing any physical system are probabilistic, has been adapted to certain areas of operations research in coal mine haulage. This paper attempts to illustrate how simulation can be used in basic haulage research and what kind of results can be expected. Optimization in this case is performed in terms of locomotive and car movement, as well as best utilization of men and equipment, and is approached primarily from the standpoint of scheduling of the main haulage. Many operational problems in mine haulage cannot be solved economically by conventional analytic or trial-error methods. However, a method of probabilistic simulation, which is based on the fundamental assumption that many of the variables governing any physical system are probabilistic, has been adapted to certain areas of operations research in mine haulage. In many physical cases several probability distributions interact with each other in special ways, and it is not possible to solve for their combined effect in a mathematical equation. This is often true in the case of mine haulage, where such variables as number of empties or loads per trip, travel times, and number of cars or tons produced in a given time are probabilistic. By using a simple example of one secondary haulage segment of a large underground haulage system, this paper attempts to illustrate how simulation can be used in basic haulage research and what kind of results can be expected. Optimization in this case is performed in terms of locomotive and car movement, as well as best utilization of men and equipment. This is the type of preliminary research that will be needed as a first phase in any major haulage study, whether it be a relatively simple economic analysis or a plan for complete automation. The problem of optimization has been approached primarily from the standpoint of scheduling of the main haulage. It is evident that the method of proba-

Jan 1, 1963

By C. W. Washburne

The waters of many oil fields have been regarded as buried sea water which has been retained in the sediments since the time of their deposition. The preservation of connate water through geological time has seemed improbable to only a few geologists, but there is room for doubt that buried sea water could remain in the strata during their periods of deformation and during the many subsequent epochs of the circulation of meteoric ground-water. Some have even suggested that the calcium chloride water in the deep mines of the Lake Superior region is ancient sea water buried in the Algonkian lavas, but it is hard to understand how such water could be derived from the highly sodic and sulphatic water of the sea. It would seem more plausible to connect the calcium chloride with the highly calcic magmas of the greenstones in which it is found. Chemical analyses of waters associated with oil differ widely from the composition of sea water, requiring extensive alteration of the latter, if the former is truly its derivative. The first notable difference is the general absence of sulphates from oil-field waters, but this has been explained satisfactorily through reduction by hydrocarbons and organic matter. Oil reduces sulphates with the production of hydrogen sulphide (or sulphur), water, and carbonates (or carbon dioxide). The second striking difference is in the high ratio of chlorine to sodium. An examination of the analyses of chloride waters from oil fields shows that they contain a large relative excess of chlorine over that in sea .water. -Moreover, there is difficulty in finding chemical reactions that are probable in nature, by which sea water could be converted into anything like the chloride waters of oil fields. In the latter a large part of the chlorine occurs as calcium and magnesium chloride. This condition might be produced by the removal of sodium carbonate, which, however, cannot be precipitated in the presence of much calcium or magnesium.

Jan 1, 1915

By C. Wegert, L. E. Paulson, S. A. Cooley, R. C. Ellman

The Grand Forks Energy Research Center (GFERC) and Commonwealth Edison of Chicago jointly conducted tests in which 400 tons of subbituminous and lignite coals were dried in a commercial scale dryer, oil sprayed and cooled, then shipped from Pekin, Ill., to Grand Forks, N.D., and stockpiled. Cars containing raw coal and dried coal which had not been sprayed, were also transported for comparative purposes. During transit, observations were made of changes in the coals' moisture content, dust losses, and temperature.

Jan 1, 1977

By F. E. Steigert, A. H. Geisler

THE permanent magnet alloy comol, which contains 17 pct Mo, 12 pct Co, balance Fe, exhibits a precipitation reaction analogous to that at the iron end of the binary Fe-Mo system. The equilibrium precipitate, (P,), has a structure isomorphous with Fe,Mo, which is rhombohedra1 with parameters a = 8.97A and a = 3038.6&apos; according to the work of Arnfelt and Westgren.&apos; In the ternary alloy the parameters are a = 8.87A and a = 31°0.5&apos;. Oscillating crystal patterns of a single matrix crystal, M, in which P, was precipitated by slow cooling from 1300°C, showed that the orientation relationship of the two lattices is as follows: (110)P3 // (110)* (111)p3 // (110)m There are crystallites of P, in 12 different orientations in a single crystal of the parent solid solution. Microscopic examination shows that the crystallites are generally plate-like with their lateral dimensions parallel to (110) matrix planes. When precipitation in a supersaturated alloy quenched from 1300°C progressed isothermally at temperatures between 600" to 800°C, the evolution of the P, structure could be traced. Diffuse diffraction effects in Laue patterns provided early evidence of the precipitation process. Analyses of these by a previously described technique2 showed that they corresponded to rod-like elements parallel to <110> matrix directions in reciprocal space. With further aging to promote growth of the precipitate, the rod-like elements contracted to points in reciprocal space for normal Bragg reflection from the precipitate as shown by the left diagram in Fig. 1. Thus the diffuse scattering was attributed to the small thickness of the plate-like particles which was inadequate for sharp diffraction. When the precipitate particles were first thick enough to give normal diffraction their structure was different from that of the equilibrium precipitate, P,. The first structure, P1, presumably is a coherent transition struc-

Jan 1, 1952

By E. A. Ernst, N. F. Carpenter

The benefits derived from an acidizing treatment are a function of the penetration achieved by the acid before complete spending. Additional penetration may be achieved by (1) controlling acid leak-08 into formation pores in the channel faces, and (2) retarding the reaction rate of the acid. A recently developed chemical additive consists of a synthetic polymeric material which absorbs hydrochloric-acid solutions, when suspended therein, swelling up to 40 times its original volume. These swollen particles have the ability to deform and seal-08 formation pores, providing fluid-loss control. In addition, they provide a diffusion barrier between the fracture face and the acid solution, prolonging the spending time of the acid. Field applications of this new technique have shown promising results. A method of conducting acid fluid-loss tests, using carbonate cores, is believed to provide fluid-loss data that are more representative of formation conditions than the conventional filter-paper determinations. INTRODUCTION The concept of oilwell acidizing has changed since its first commercial application, 30 years ago. Originally, it was visualized that the acid penetrated thousands of tiny pores and flow channels in the matrix rock, enlarging them by dissolving the carbonate walls. The resultant permeability increase was assumed to be the responsible factor in increasing production from the well. Recent laboratory studies,&apos; however, have shown that this does not provide the complete picture. Although this type of individual pore penetration by the acid does take place during acid "soaks", designed to overcome "skin effect" due to mud invasion in the immediate vicinity of the wellbore, many years of experience have shown that considerable pressure is required to attain any appreciable injection rate into the fine capillary pores of the rock. During most acidizing treatments, the bottom-hole pressure build-up due to the restriction of flow into the formation exceeds the "breakdown" pressure of the rock so that a fracture is induced. In most cases, such fractures open up along natural, incipient fissures and zones of weakness in the rock and, therefore, tend to follow the natural stress pattern of the rock—whether it be horizontal, vertical or inclined. Because of the comparatively greater permeability of the channel in relation to that of the matrix, the bulk of the acid volume is diverted into the newly opened fracture. Here it quickly penetrates the formation, opening and ex- tending the fracture in much the same manner as a conventional fracturing fluid. Unlike the fracturing fluid, however, most acidizing solutions contain no propping agent; thus, the open fracture will again close when the injection pressure is relieved. Laboratory studies2 have shown that in many cases the etching of the fracture faces, resulting from the reaction between the acidizing solution and the carbonate rock, is nonuniform due to the heterogeneity of the rock structure. As a result, the two fracture faces no longer match when pressure is released, and support pillars and intermediate voids remain, forming a high-conductivity channel for well fluids. Unfortunately, this is not true over the entire area of the fracture, but only over that portion of the fracture where the rock has been partially dissolved by the acid. The acid solution spends as its travels away from the wellbore; once it has completely spent, even though it may provide additional mechanical fracture extension, no additional benefit due to etching of fracture faces can be expected. Studies of acid reaction rates under formation conditions,3 observing the effect of different variables upon spending time, have shown that the reaction was often so rapid that very little penetration of the formation occurred before the acid was spent. Study was undertaken to devise methods of increasing the penetration of the acid before spending, so as to provide greater benefit from the acidizing treatment by etching a greater portion of the fracture faces. Several techniques were devised to accomplish this purpose. First, chemical additives were developed which were designed to retard the reaction rate of the acid, causing it to penetrate a greater distance from the wellbore before finally becoming spent. Another method was to increase the injection rate of the acid. However, it was found that the resultant increased shear tended to accelerate the reaction rate of the acid, partially offsetting the benefits of the higher injection rate insofar as achieving increased penetration before spending was concerned.&apos; Another approach to the problem of achieving increased penetration was the development of fluid-loss additives for acid solutions, which would minimize the volume of acid lost into formation pores in the fracture faces and provide maximum fracture extension for the volume of acid injected during the treatment. The use of fluid-loss additives is now considered the most effective method of providing maximum fracturing-fluid efficiency.~ Unfortunately, this latter technique does not solve the problem of rapid reaction rate, with consequent limitation of the fracture area benefited by reaction with unspent acid. A newly developed acid additive overcomes many of these limitations by providing the dual benefits of fluid-loss control and mechanical retardation of acid reaction

By J. F. Stiehr, R. L. Sanford, T. L. Myers

This paper summarizes the development of a Directory of Computer Programs Applicable to US Mining Practices and Problems. The directory is funded by the US Bureau of Mines and includes a sampling of computer usage in operating and manufacturing companies, consulting firms, computer companies, research organizations, universities, and various US government agencies. General references to computer applications throughout the mining industry are discussed as well as the availability of programs to interested organizations or individuals.

Jan 9, 1979

By A. J. Stosick, J. R. Hoffman, E. Rudy, St. Windisch

The binary alloy system Mo-C zoas investigated by means of X-ray, metallog/aphic, thermoanalytical, and melting-point techniques on chemically analyzed specimens. The system, Fig. 39, is characterized by three congruently melting, intermediate phases, Mo2C, n MoCi-x, and aMoC1-,, of which only Mo,C is stable at temperatures below 1650°C. Substoichio-metrzc (~32.5 at. pct C) dimolybdenum carbide undergoes a homogeneous sublattice order-disorder transformation at temperatures of approximately 1400°C, whereas hyperstoichiorrletric compositions undergo a discontinuous Phase change. The order-disorder transitions in the Me, C phases are discussed in terms of the structural changes involved in the transformation processes and the absence of long-range sublattice coherency in stoichiometric or hyperstoiclziomet-ric compositions attributed to the impossibility of obtaining long-range order in a linear chain of alternating carbon atoms and vacancies. From the experimental phase relutionships and the known thermody-namic data for Mo2 C, limits for the free energies of formation for the high-temperature phases r) MoC1-, and aMoC1-, are deriued and found to be in good agreement with data previously obtained from phase equilibria in ternary metal-carbon systems. IN the course of studies of the high-temperature phase relationships in ternary systems of refractory transition metals with carbon,&apos; a number of inconsistencies found in previous work necessitated a reex-amination of some of the related metal-carbon binaries. A reassessment of the binary system data also seemed

Jan 1, 1968