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By C. B. Richardson, R. D. Sprague

The year 1938 was the most active and successful in the history of the oil industry in southern Louisiana. Drilling showed a 16 per cent increase over that of 1937, with a total of 538 wells drilled, which yielded 315 oil wells, 19 distillate wells, 4 gas wells and 200 dry holes. Nineteen new fields were discovered during the year, all but three of which were completed by plugging back to sands previously drilled through. Electrical logging played a large part in these new discoveries as well as in the discovery of new sands during routine development of fields. Fourteen of the new discoveries produced oil, and five produced only gas and distillate. Southern Louisiana continues to lead the world in depth of drilling, which is in part due to the great thickness of comparatively young deltaic sediments near the coast and the existence of numerous sands. The present development is rather evenly distributed over a coastal strip 100 miles wide. New Fields North Tepetate, Acadia Parish.—Atlantic Refining Company's No. 1 Klumpp was completed for a new field through perforations from 7960 to 7970 ft. The initial production was 65 bbl. of 54" gravity distillate and 4 million cubic feet of gas daily through a 1/4-in. choke with tubing pressure of 2850 Ib. and casing pressure of 2930 lb. The well is in see. 12, 7 S., 2 W., just north of Tepetate field. It was drilled to a depth of 8705 ft. and plugged back for its final completion. Atlantic's NO. 2 was completed in a new sand at 8300 ft., also for distillate. South Crowley, Acadia Parish.—Humble Oil and Refining Company's No. 1 Boyd Finch was completed in July 1938, as an oil well through perforations from 7318 to 7325 ft. after plugging from a total depth of 10,222 ft. After making several hundred barrels of oil, the well went to

Jan 1, 1939

By Carl J. Christensen

This paper presents the development of diamond coring of the Weber sand section in the Rangely Field, Colorado. The description and operation of the diamond-coring equipment is included as well as the economics and results obtained by its use. Diamond coring is compared with the other methods used for drilling the Weber sand. Two types of diamond coring are discussed. The first and the one used most extensively is the regular 6 ?x 3¾-in. diamond bit and bottom hole 50-ft barrel. The second type, which has also been used successfully by Stanolind, consists of a 4 13/16 x 2 11/32-in. cutting bit and reverse circulation coring equipment. The first type will be referred to as regular or conventional diamond coring while the latter type will be referred to as reverse circulation diamond coring. Introduction Diamond coring has been used for many years in mines, quarries, surface coring at dam sites, laboratory work, and so on, but, until recently, had never been used very extensively in coring oil sands and other oil-bearing strata. It was demonstrated early in its development that hard forma-tions could be cut rapidly and that core recoveries far exceeded those obtained with conventional hard rock bits and quite often 100 pet recovery was obtained. However, the poorly constructed diamond-coring equipment and resulting high costs of early diamond coring slowed down its progress. Early in the development Of the Rangely Weber field, Rio Blanco County, Colorado, the Rangely Engineering Committee selected key wells that were to core the Weber section in its entirety. These cores were to be analyzed and various sections tested to gather sufficient information so that accurate reservoir studies could be made. The number of wells selected were kept at a minimum inasmuch as the productive Weber section, which is found at an approximate depth of 6000 ft, is thick, being as much as 600 to 700 ft on top of the structure. The Weber section is also comparatively hard to drill. For instance, one well took 60 days to core 490 ft of Weber sand with conventional coring equipment. It was noticed, however, that Core Labora-verse diamond plug cutter could quickly cut a plug from. one of these hard cores. This fact led to the serious consideration of diamond coring the Weber sand. The first diamond coring at Randy was performed by Stanolind in August 1946 andl although we experienced some difficulties, the results definitely indicated that diamond coring would be successful at Rangely for .coring the Weber sand. As more wells were cored and the equipment improved somewhat, diamond coring became less expensive than drilling the Weber sand with the conventional rock bit. In less than one Year diamond coring has definitely Proved its usefulness in oil-field drilling operations in the Rocky Mountain area where formations quite often drill very hard. The practice of spot coring in hard oil-bearing formations with conventional coring equipment is giving way diaimond coring of the entire sections, thus givng an operator the complete picture.

Jan 1, 1948

By Carl J. Christensen

This paper presents the development of diamond coring of the Weber sand section in the Rangely Field, Colorado. The description and operation of the diamond-coring equipment is included as well as the economics and results obtained by its use. Diamond coring is compared with the other methods used for drilling the Weber sand. Two types of diamond coring are discussed. The first and the one used most extensively is the regular 6 ?x 3¾-in. diamond bit and bottom hole 50-ft barrel. The second type, which has also been used successfully by Stanolind, consists of a 4 13/16 x 2 11/32-in. cutting bit and reverse circulation coring equipment. The first type will be referred to as regular or conventional diamond coring while the latter type will be referred to as reverse circulation diamond coring. Introduction Diamond coring has been used for many years in mines, quarries, surface coring at dam sites, laboratory work, and so on, but, until recently, had never been used very extensively in coring oil sands and other oil-bearing strata. It was demonstrated early in its development that hard forma-tions could be cut rapidly and that core recoveries far exceeded those obtained with conventional hard rock bits and quite often 100 pet recovery was obtained. However, the poorly constructed diamond-coring equipment and resulting high costs of early diamond coring slowed down its progress. Early in the development Of the Rangely Weber field, Rio Blanco County, Colorado, the Rangely Engineering Committee selected key wells that were to core the Weber section in its entirety. These cores were to be analyzed and various sections tested to gather sufficient information so that accurate reservoir studies could be made. The number of wells selected were kept at a minimum inasmuch as the productive Weber section, which is found at an approximate depth of 6000 ft, is thick, being as much as 600 to 700 ft on top of the structure. The Weber section is also comparatively hard to drill. For instance, one well took 60 days to core 490 ft of Weber sand with conventional coring equipment. It was noticed, however, that Core Labora-verse diamond plug cutter could quickly cut a plug from. one of these hard cores. This fact led to the serious consideration of diamond coring the Weber sand. The first diamond coring at Randy was performed by Stanolind in August 1946 andl although we experienced some difficulties, the results definitely indicated that diamond coring would be successful at Rangely for .coring the Weber sand. As more wells were cored and the equipment improved somewhat, diamond coring became less expensive than drilling the Weber sand with the conventional rock bit. In less than one Year diamond coring has definitely Proved its usefulness in oil-field drilling operations in the Rocky Mountain area where formations quite often drill very hard. The practice of spot coring in hard oil-bearing formations with conventional coring equipment is giving way diaimond coring of the entire sections, thus givng an operator the complete picture.

Jan 1, 1948

By Frank W. Harris

THE strength of hard drawn copper wire is a question of considerable importance to both manufacturer and consumer. Unlike steel and alloy wires, in which strength is governed by both chemical and physical considerations, the high conductivity required for copper wire in the electrical industry generally precludes the possibility of obtaining tensile strength through the use of alloys. Consequently, this strength is largely a matter of the physical structure, and all factors known to affect this structure, such as rolling temperature, die contours, lubricants, drawing speeds, etc., are matters of prime importance. The experiments described here have been carried out during the past year at the Baltimore plant of the American Smelting & Refining Co., in connection with a general investigation of some of the questions mentioned above, with the object of studying the physical structure of hard drawn copper wire and the influence of certain factors on that structure. The work has been of an exploratory nature, rather than comprehensive, but it was thought that the results might prove of sufficient general interest to warrant their publication. The bulk of the hard drawn copper wire used in places where strength is an important factor is manufactured to strict specification, based usually in the United States on that of the American Society for Testing Materials (B-1-23). This specification calls for almost as high a value of tensile strength, consistent with elongation, as it is possible practically to obtain, and only physically perfect material can be relied on to meet such a specification. Obvious defects, such as laminations produced through fins in the original rods or brittleness due to overdrawing, are usually recognized and need only passing reference. Laminations can be detected by twisting and untwisting the wire several times; they will show up on the surface in the form of fins. Fig. 1 shows a very bad example of this defect. The wire may be perfectly smooth before twisting but when such laminations are present they will readily show up under this treatment. This trouble is caused by similar defects in the original rod produced by overfills in rolling. Fig. 2 shows the cross-section of the rod from which the wire in Fig. 1 was drawn.

Jan 1, 1928

By Frank Harris

THE strength of hard drawn copper wire is a question of considerable importance to both manufacturer and consumer. Unlike steel and alloy wires, in which strength is governed by both chemical and physical considerations, the high conductivity required for copper wire in the electrical industry generally precludes the possibility of obtaining tensile strength through the use of alloys. Consequently, this strength is largely a matter of the physical structure, and all factors known to affect this structure, such as rolling temperature, die contours, lubricants, drawing speeds, etc., are matters of prime importance. The experiments described here have been carried out during the past year at the Baltimore plant of the American Smelting & Refining Co., in connection with a general investigation of some of the questions mentioned above, with the object of studying the physical structure of hard drawn copper, wire and the influence of certain factors on that structure. The work has been of an exploratory nature, rather than comprehensive, but it was thought that the results might prove of sufficient general interest to warrant their publication. The bulk of the hard drawn copper wire used in places where strength is an important factor is manufactured to strict specification, based usually in the United States on that of the American Society for Testing Materials (B-1-23). This specification calls for almost as high a value of tensile strength; consistent with elongation, as it is possible practically to obtain, and only physically perfect material can be relied on to meet such a specification. Obvious defects, such as laminations produced through fins in the original rods or brittleness due to overdrawing, are usually recognized and need only passing reference. Laminations can be detected by twisting and untwisting the wire several times; they will show up on the surface in the form of fins. Fig. 1 shows a very bad example of this defect. The wire may be perfectly smooth before twisting but when such laminations are present they will readily show up under this treatment. This trouble is caused by similar defects in the original rod produced by overfills in rolling. Fig. 2 shows the cross-section of the rod from which the wire in Fig.1 was drawn.

Jan 1, 1928

By V. N. Mackiw

IN the process employed by Sherritt Gordon Mines Ltd. for the production of metallic nickel, a sul-fide concentrate is leached with ammonia and air under pressure. Following the removal of iron, copper, and other impurities, there remains a purified solution having the following analysis: 40 to 50 g per liter Ni, 200 to 400 g per liter (NH4)2 SO 4, and 20 to 30 g per liter NH3. Metallic nickel is reduced from this solution by hydrogen under pressure at 300' to 350°F in mechanically agitated autoclaves. A catalyst, ferrous sulfate, is required to initiate the first reduction. After the reduction, the depleted solution is discharged, leaving the metallic nickel in the autoclave. The nickel produced, being in a finely divided form, is used as a catalyst for the reduction of the next batch of solution. Upon repeated use the metallic nickel particles increase in size and become more compact, resulting in the production of a powder with higher apparent density. For this reason, each reduction is termed densification. Finally, when the burden of metal powder in the autoclave becomes too great to obtain effective agitation, both powder and depleted solution are discharged. The autoclave is then filled with fresh solution, ferrous sulfate catalyst added as before, and a new cycle started. The operation is described in earlier publications.1-6 A comprehensive historical review of the reduction of metals from solutions in general was given in a paper by Schaufelberger.7 The experimental data presented in this paper were taken from the work done in the Research Laboratory of Sherritt Gordon Mines Ltd. in Ottawa during the development of the process in 1951 and 1952. The results of the work were tested on a pilot plant scale in Ottawa in the period 1952 to 1953. Following laboratory and the pilot plant studies a commercial process has operated successfully since 1954 in the Nickel Refinery of Sherritt Gordon Mines Ltd. in Fort Saskatchewan, Alberta. General Experimental Technique The experiments were carried out in a stainless steel, 1-gallon, agitated autoclave designed and manufactured by Autoclave Engineers Inc. The inside dimensions of the vessel were 5 in. diam and 12 in. depth. The stirrer consisted of a 1/2 in. diam shaft 11 in. long fitted, with an axial flow type impeller (three blades bent to throw downwards) and a radial flow

Jan 1, 1958

By Clinton M. Ball

Magnetic iron-ore is found in many localities throughout this and other countries, in large bodies and in convenient proximity to other materials required for its conversion into iron and steel; and these bodies of ore would have great commercial value on account of their nearness to consuming markets if they were generally suitable in their natural state for use in the larger operations of steel-making. In the manufacture of iron and steel it has been found, however, that not all ores are equally valuable as sources of raw material for the finished products of furnace, forge and foundry; and, as is now well understood, this is because of the intrusion, in the process of formation of the ore-bodies, of substances which can enter into deleterious combinations with the iron itself, or form compounds associated with the iron oxide which will hinder, if they do not altogether prevent, the production therefrom of the higher grades of finished metal. It is only since the development of the modern method of steel-making by the Bessemer process that the art of the chemist has been called to a critical study of the nature and effect produced by the presence of these pernicious substances in the furnace while the iron is undergoing reduction to the metallic state. Phosphorus and sulphur are the most common and obnoxious elements, and the admixture of one or the other, or both of these, in small percentages and varying proportions, will greatly modify the final results of manufacture. It so happens that generally, although not always, these hurtful elements are found in compounds in the ore which are not magnetic, and this circumstance has led to the expenditure of much ingenuity and money over a long period of time, in attempts to utilize the attractive power of magnets to separate the magnetic oxide of iron out of its crushed ores and from sands, in

Jan 1, 1896

By H. S. Munroe

AN elaborate discussion under this heading formed a chapter in one of the reports made by Professor Raymond as Commissioner of Mining Statistics.* In a subsequent report- was printed a paper, by Mr. William Main, Jr., of Columbia, South Carolina, containing a theoretical investigation into the effect of the velocity of impact on the effective ditty of stamps. A visit to the Lake Superior copper region last summer suggested an inquiry into the relative efficiency and economy of the enormous steam stamps of the copper-mills, as compared with the results obtained with the cant and tappet stamps commonly used in the West. The atmospheric stamp used at the Phoenix Mill promised to add interest to the inquiry, as giving an example of unusually high speed, this stamp making 160 drops per minute. In introducing his subject Dr. Raymond makes the following remarks, which are quite apropos of the present investigation : "In considering the economical application of stamping machinery, we meet, at- the beginning, with serious difficulties in obtaining accurate data for comparison. The weight and fall of stamps vary as the shoes and dies wear out; and this may lead to a change of speed also. Moreover, defects in engines, boilers, or machinery for the transmission of power, may occasion serious losses, which cannot fairly be charged to the arrangements of the stamps proper. Again, the capacity of stamp-mills is directly dependent, in some degree, upon the nature and extent of discharge, fineness of screens, and other peculiarities of the battery. Finally the hardness and tenacity of the rock crushed varies so much that comparisons between different localities cannot be implicitly trusted. The safest experiments are those made in the same mill, by changing first one and then another condition of working; but this is seldom possible for such * Mineral Resources West of the Rocky Mountains, 1871, p. 380. †- Mineral Resources West of the Rocky Mountains,, 1873, p. 345.

Jan 1, 1881

By C. H. Li, R. J. Stokes, S. H. Bendel, J. A. Sartell, T. L. Johnston

The mechanism of the oxidation of high-purity copper has been studied at temperatures from 500° to 981°C employing gravimetric, high-temperature microscopic and inert marker techniques. An investigation of the adhesion of copper oxides was also made. The oxidation of copper is found to be parabolic at all temperatures. It is concluded that the controlling mechanism is the outward diffusion of CU+ ions through the Cu2O layer, but the mechanism of diffusion is modified by the state of compressive stress in the oxide layer at the oxidation temperature. At temperatures below the transition from elastic to plastic behavior of Cu2O the growth stresses reach a value sufficiently high to cause CuO whiskers to be extruded. The extrusion of whiskers results in the injection of a large number of vacancies into the CuO. The Cu20 layer grows by the advance of the CuzO/CuO interface into vacancy-rich CuO. Since there is an adequate supply of non -thermally created vacancies, the activation energy for oxidation is that required to move the Cu+ ion through the appropriate saddle point to a neighboring vacancy, which has been determined to be 20,000 cal per mole. At temperatures at which the Cu20 can deform plastically the stresses are never high enough to cause whiskers to form. thus vacancies must be supplied by themal activation and as a result the activation energy increases to 40.000 cal per mole. ALTHOUGH extensive studies of the oxidation kinetics of pure copper have been made in the past. the mechanism has received relatively little attention. As a result, certain features of the kinetic data have not been satisfactorily explained' For example, several workers1,2 have reported that the activation energy for oxidation in the range from 500° to 700° C was about 20,000 cal per mole whereas that above

Jan 1, 1960

By R. J. Schilthuis, T. V. Moore

In a previous paper,' the results of some experimental work on the measurement of slippage in the flow of oil and gas mixtures through vertical pipes were presented. The data obtained were correlated and equations were deduced from which the performance of the experimental gas-lift could be predicted with reasonable accuracy. However, attempts to apply the equations to the calculation of pressure drops in actual flowing wells yielded erroneous results. At the time the results of the experimental work were published, no satisfactory explanation could be offered for the failure of the empirical equations to express properly the performance of wells. However, recent work has led to the development of a new hypothesis which presupposes certain conditions affecting the flow of oil and gas in wells. When the proposed equations are corrected to allow for these conditions, an agreement between the observed and calculated performance of the actual wells is obtained which in most cases is quite satisfactory, although it is subject to certain limitations. In this paper, the method of calculating the pressure drop in actual wells is considered, and the application of the method to the design of tubing is discussed. (For nomenclature used in this discussion, see Table 1.) Factors Affecting Slippage and Efficiency At the outset, a few of the principle factors affecting slippage and efficiency in the gas-lift discussed in the previous paper will be reviewed. In the flow of the mixture of oil and gas in a vertical pipe, slippage is the phenomenon of gas moving upward with a. linear velocity greater than that of the oil. Under steady conditions, if given quantities of oil and gas enter the tubing per unit of time, the same quantities of oil and gas per unit time must, on the average, pass every section of the tubing; otherwise, there would be accumulation or depletion of the oil or gas at some sections, and the flow would be unsteady. Therefore, if the gas is to flow at a greater linear velocity than that of the liquid,

Jan 1, 1933

By F. M. Lewis, J. E. Goodman

A larger, slow-speed, under-loaded ball mill and hydraulic classifier have almost doubled grinding efficiency at the lsabella mill. TENNESSEE Copper Co. operates two ore con-A centrators, the London and Isabella mills near Copperhill, Tenn. In 1948 and 1949 the small ball mills and rake classifiers in the London concentrator were replaced by one large ball mill and one hydraulic classifier. This new ball mill was designed oversize so that it could be operated at slower than normal speed. The proper operating conditions were established and the results published.' Later it was found that this mill operated more efficiently with a small ball charge." While this London grinding practice was being developed, the Isabella grinding circuit was not changed in any way. It remained a conventional two-stage rod mill—ball mill combination, the rod mill in open circuit and the ball mill in closed circuit with a rake classifier. Study of the data indicated that grinding cost could be lowered by converting to the London practice, but not enough would have been saved to warrant the expense of converting. No plan for improving this grinding operation could be developed. In 1953 this study was reopened when plans were made to increase the Isabella mill output from 1150 to 1500 tpd. At this time the grinding circuit consisted of a 6x12 rod mill followed by a 6x12 ball mill in closed circuit with a 6-ft rake classifier. Another 6x12 ball mill and 6-ft rake classifier would have been sufficient equipment and would have been the simplest and cheapest installation. However, this would have offered no improvement in grinding efficiency or operating cost. If, on the other hand, the grinding operation could be converted to the London practice, by installation of one large 101/2x9x9 tricone mill and a 10-ft hydroscillator,2 lower operating costs would justify the additional investment. Economics: Table I presents estimates for the two schemes for enlarging the Isabella mill. In the first scheme, column 1, one 6x12 ball mill and one 6-ft rake classifier were to be added. In the second scheme, column 2, the existing small ball mill and rake classifier were to be retired and one large mill and hydroscillator were to be installed. Estimated savings from the difference in operating costs made an attractive return on the additional investment for the large mill and hydroscillator. Actual costs of carrying out this plan are tabulated in column 3b. It will be seen that these costs follow the estimates in column 3a very Closely. The return on the additional investment is calculated from the difference in the operating cost in column 1 and the actual operating cost in column 3b. This too come very close to the estimate. Power and Steel: Power requirements and steel consumption for the rod mills and ball mills, both actual and estimated, are presented in Table 11.

Jan 1, 1958

By R. C. Temps, G. E. Aiken

Compania de Acero del Pacifico, S.A., the sole Chilean steel producer, is adding to the expanding Chilean economy with development of the El Algarrobo mine. Expected to go on stream early in 1962, Algarrobo is a conventional open pit mine that will include facilities for ore extraction, crushing and screening, rail transport to the harbor at Huasco, modern ship-loading equipment and maintenance shops. CAP anticipates producing 1.38 mil- lion tons annually of high-grade ore for national and world market consumption. Chilean and North American management and engineering teams combined more than a decade ago in the financing and building of CAP'S Huachipato integrated steel plant. A similar performance is being achieved in northern Chile near the town of Vallenar with the opening of a 50-year supply of iron ore from the Algarrobo deposit. This successful intra-American undertaking deserves special mention in these times when some U.S. foreign assistance programs must be defended, particularly with respect to Latin America. North American financial participation in Algarrobo, through the Export-Import Bank of Washington, represents the greatest portion of the $24 million being invested.

Jan 3, 1962

By R. H. Richman

Coarse-grained Fe-Ni-C martensites formed at subzero temperatures were strained in compression at room temperature and the plastic deformation modes examined as a funclion of carbon content. At very low carbon levels, defovmation occurs hy wavy slip; commencing at about 0.05 pct C, mechanical twinning accounts for an increasing proportion of the plastic flow. Beyond approximately 0.4 pct C the deformation appears to be entirely by mechanical twinning. The habit planes of the operative twin modes were determined to be (113), (0131, and "(089)" in decreasing frequency of occurrence. Some of the implicaticms of Ihe o6served deformation modes upon the structure and properties of ferrous martensites are discussed. METALLURGISTS have long sought to explain the mechanical properties of ferrous martensites, particularly the extraordinary hardness and strength of the high-carbon varieties. Until recently the lack of precise knowledge of the structure of martensite crystals was the most serious barrier to understanding; however, the advent of thin-foil techniques for transmission electron microscopy has removed much of the mystery from martensite structure. Observations by Kelly and Nutting,"' and many others since, indicate that Fe-C based martensite crystals are internally twinned to a degree dependent upon the carbon content, and that a martensite plate containing 0.8 wt pct C or more consists of a stack of twin-related lamellae with each lamella on the order of l00A thick. Such a structure would be expected to influence greatly all aspects of metallurgical behavior, and many of the properties of Fe-C based martensites have been rationalized accordingly. Recent independent experiments led Winchell and cohen3 to conclude that the strength of ferrous martensite is derived primarily from solid solution hardening of the iron lattice by interstitial carbon atoms. Strength contributions from precipitation, dislocation-atmosphere interactions, clustering, short-range order, crystallite size, and so forth, were considered to be of secondary importance. In the view of Winchell and Cohen, the twinned structure of martensite serves mainly to limit the effective length of dislocation lines in the lattice, and thereby confers an added measure of hardening. Few properties of metallic crystals are as sensitive to metallurgical structure as are deformation mechanisms. It is somewhat surprising therefore, that, except for metallographic evidence of mechanical twins in strained martensite,4 no systematic examination of plastic deformation

Jan 1, 1963

By Joseph Kuti

Longwall mining is the term used for the underground extraction of a wide and deep panel of coal. Such a panel may be blocked out by one or more entries on either side ("head" and "tail") of a longwall face. If all the entries are pre-driven, the panel extraction is termed longwall retreat mining. With one exception, all the longwall faces in the United States are of this type3 Prior to the general decline in the rates of production with Continuous Miners, the development of the multiple entries generally kept ahead of the longwall extraction rate. This is no longer the case: longwall extraction rates far exceed the rate of development. In addition to this problem, in newly established mines, the development of a haulage and bleeder system based on multiple entries results in a lead-time of three years or more before longwall mining can be applied. This is one reason why earlier projections and much of the optimism attached to longwall mining as a principal "savior" in the energy crisis should be viewed with some caution. The alternatives to retreat mining with multiple entries are: Modified retreat mining- where the tail-entry is being formed during the mining of-the panel ("2"-system). Some form of advance mining-where the head-entry or both head and tail entries are being formed as part of the longwall extraction process. These methods are well-known and well-established. Variants of them are being practiced in Canada, Central and South America, but not in the US. It is primarily the laws governing ventilation-conceived for room and pillar mining which prevent the rapid development of these techniques. Another aspect of longwall mining is that it requires a systematic and consistent approach in organization, roof control, ventilation and transport. It is for this reason that compliance with health and safety regulation is fairly well ensured if the longwall system has been well laid out and is subsequently well-run. Nevertheless, a management mentality raised in the great flexibility of the room and pillar system cannot always come to terms with the degree of forward planning and rigid discipline required to successful longwall mining. Research, development and other investments in the partial aspects of longwall mining are always of interest, but no massive trend to longwall can be expected realistically unless these major stumbling blocks in the basic law and basic approach are effectively removed.

Jan 1, 1980

By J. A. Roberson, Robert A. Rapp

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

Jan 1, 1968

By M. E. Wadsworth, T. L. MacKay

Sintered UO, samples were leached in sulfuric acid solutions of various concentrations. A pressurized system was used so that it was possible to investigate the kinetics of the reaction to 270°C with oxygen overpressures as high as 900 psi. The rate was observed to be a function of the concentration of hydrogen ions and directly proportional to the partial pressure of oxygen. Evidences are presented which indicate that a UO2 surface site reacts with a molecule of water to form a hydroxyl complex which in turn can dissociate with the characteristics of a weak acid. A rate determining step has been proposed which involves the reaction between an oxygen molecule and the hydroxyl complex on the surface of UO,. ThE 2 principal methods for uranium dissolution are carbonate and acid leaching. The sulfuric acid leach is the more popular and is used for the treatment of the majority of the ores of Africa, Canada, and the United States. Low recoveries in basic leach circuits led investigators at the University of British columbia1 to study leaching of uranium ores in pressurized vessels. Early in the study of dissolution of uranium it was found that only uranium in the hexava-lent state could be leached in acid or basic circuits. Therefore, the use of oxygen over-pressure in an autoclave offered an interesting approach to solving the low recovery problems of carbonate leaching. UO, was used in this study because it could be obtained in high purity and also because it is representative of the most refractory of the primary uranium minerals. A pressurized system was used to provide a means whereby important temperature and pressure parameters could be varied for the evaluation of the kinetic processes. The mechanism for the dissolution of UO2 should be similar for any of the uraninite type minerals. At the present all of the kinetic studies that have been conducted have been in carbonate media. Peters and Halpern2 carried out a kinetic study of the leaching of pitchblende. Their specimens were pitchblende ores selected on the basis of high grade and homogeneity. Pearson and wadsworth3 conducted a kinetic study of the dissolution of UO2 in carbonate solutions with results very similar to those obtained by Peters and Halpern. EXPERIMENTAL The UO2 as received* was found by spectroscopic *Mallinckrodt reagent, supplied by the Atomic Energy Commission. analysis to have a purity of 99.94 pct 0.03. It was ground in a mechanical agate mortar and screened through a 400-mesh sieve. Thin flat disks of UO2 were prepared by pressing the sized powder in a specially constructed die at a total pressure of approximately 25 tons per sq in. The pressed disks were approximately 0.25 cm thick, 1.6 cm diam, and 3.5 g in weight. As pressed, the samples were approximately 65 pct of theoretical density. It was essential that a binder such as poly-vinyl alcohol be added before pressing to prevent formation of cracks when fired. It was found by trial and error that pressed disks sintered close to 1870°C in a hydrogen atmosphere, reach densities between 91 and 91.5 pct of the theoretical density. At this density the samples had no measurable porosity based upon a 2-hr emersion in boiling water. An X-ray examination of these sintered UO2 disks showed them to be identical with the original UO2 received. Reaction of UO2 with the alundum furnace core was prevented by placing molybdenum between the samples and the core according to the method of Corwin and Eyerly.4 Leaching studies were carried out in a specially designed autoclave, the details of which have been presented e1sewhere.6 The main features of the equipment as applied to a kinetic study are: 1) solution samples may be removed during the course of a single run; and 2) temperature and agitation are carefully controlled. Two-ml samples removed from the autoclave during the course of a run were analyzed for U3O8 content with a Beckman model DK-2 spectrophotometer by the method of

Jan 1, 1959

By R. Gibala

Internal-friction measurements on hydrogen-charged iron over the temperature range 4° to 300°K are reported. Two relaxation peaks, the hydrogen Snoek peak at 48 °K and the hydrogen cold-work peak in the range 145" to 2200K, are observed at 80 kc per sec. The effects of hydrogen-charging, aging, and deformation on the internal-friction results are determined and are used to show evidence of partitioning of hydrogen between solid solution and dislocations. The hydrogen-dislocation binding energy is estimated from the behaviors of the relaxation tiwzes and relaxation strengths of the Snoek peak and the cold-work peak. Its value is approxi,mately 6400 cal per mole. MANY investigators have demonstrated the usefulness of internal-friction measurements in determining the manner in which interstitial impurities interact with dislocations in bcc metals. Part of this success has resulted from the existence in bcc interstitial alloys of two anelastic relaxation peaks—the Snoek peak' and the cold-work or Koster peak2 (designated hereafter by SP and CWP, respectively). The SP has its origin in the redistribution of interstitials in solid solution among sites made energetically nonequivalent by an applied stress. The rate at which the redistribution occurs, measured by the relaxation time for the process, is related in a simple way to the diffusion rate of the interstitial in the free solution. The relaxation strength is proportional to the concentration of interstitial in solid solution. The CWP appears to have its origin in the relaxation of an interstitial-dislocation complex for which the relaxation time at a given temperature is much longer than that for the SP. The relaxation strength depends strongly on the concentration of interstitial and the amount of deformation at relatively low concentrations and deformations.2-8 From the dependence of the relaxation strength on interstitial concentration, the SP and CWP may serve as measures of the concentrations of interstitials in free solution and bound at dislocations, respectively. Thus their behaviors have been used to investigate interstitial-dislocation interactions in Fe-C, Fe-N, and several refractory metal systems.'-' However, the Fe-H system has not been studied extensively,? even though disputes in recent years over the mechanism of hydrogen embrittlement in steels involve argument over the extent to which lattice hydrogen and hydrogen-dislocation interactions play an important role.?-'' Previous work on Fe-H indicates the internal-friction behavior to be qualitatively consistent with that for other systems. Apparently, both a SP and a CWP are observed in the temperature ranges 30" to 50°K and 100°to 140°K, respectively (at 1 cps). However, there is neither sufficient nor accurate enough information to identify convincingly these peaks with their supposed counterparts in other systems. Nor have there been any attempts to make quantitative use of these peaks to study hydrogen diffusion, aging, or interaction processes. In this paper, an attempt is made to obtain more complete information on internal friction of hydrogen in iron than presently available. Internal-friction measurements in the range 4° to 300°K on hydrogen-charged iron show that the two peaks discussed above are in fact the hydrogen SP and CWP. Several effects of hydrogen charging, aging, and deformation on these peaks are observed and are used to determine the partitioning of hydrogen between solid solution and dislocation sites in iron. EXPERIMENTAL Materials. The starting material for this investigation was a high-purity iron supplied by National Research Corp. as a 1-in.-diam rod. The following analysis was given (inwt pct): C, 0.004; N, 0.0003; 0, 0.007; P, 0.002; S, 0.005; Si, 0.006; Mn, 0.001; Cu, 0.002; Ni, 0.005; Cr, 0.001; Mo, 0.001. After an initial vacuum anneal (-5 XTorr) at 700°C, the rod was cold-

Jan 1, 1968

By D. Cox, M. J. Duggin, L. Zwell

The carbides of approximate composition and Mn have been studied using X-ray diffraction techniques. Those carbides of the type (Fe,Aln)zC ave isostructural with cementite. The cell pararmeters a and c have minimum values at approximately 10 at. pd substitution of manganese for iron; no satisfactory explanation has yet been found for this phenomenon. The carbide fFeMn4)C has a monoclinic unit cell whose dimensions are close to those of ,11,15Cz A neu-troip-dij~ractiot~ study of (F'eAlrz4)C~ reveals that, like MnsCZ, it is isostructural with Pd5Bz. The iron and manganese atoms occupy the palladium atom sites, while the carbon atoms were found to have the same atomic coordinates as the hovon atoms. A neutrorr-diffraction study of indicates that the carbon-atom positions are very close to those occupied in (Fez.,ll/lr~,.3)C. In both carbides studied, tlre iron and manganese atomzs were found to be essentially randomly distributed, although, in the case of (Fe,.811fn1.2)C, it is possible that there may be a slight preference of manganese atoms for- the general (d) positions and a corresponding slight preference of iron atoms for the special (c) positions. It has been found that a complete range of solid solution exists between Fe3C and Mn3C at 1050°C,I although Mn3C becomes unstable when the temperature is reduced to 95O0C,' and can only be retained by rapid quenching. It is also known that a complete range of solid solution exists from Fe5Cz to M~SC~,~ although the stability range of carbides of the type (Fe,Mn)sCz as a function of the relative proportions of iron and manganese is not known. X-ray examinations of Oh-man's carbide3 and Spiegeleisenkristall,~ which have the approximate compositions (Fe3.67Mnl.33)C2 and (Fe3-,Mn,)C, where x lies between 0.4 and 1, respectively, have been made. The following carbides have also been studied: ] The lattice parameters determined during these investigations are listed in Table I. It is seen that carbides of the type (Fe,Mn)sCz have a monoclinic unit cell while carbides of the type (Fe,Mn)3C have an orthorhombic unit cell. It is evident that the variation of lattice parameters with manganese content is not linear for carbides of the type (Fe,Mn)3C. The coordinates of the atoms in (Fe2.7Mno.3)C have recently been determined by single-crystal analysis., The fractional atomic coordinates have been shown by Fasiska and jeffrey to be in good agreement withj those deduced from an earlier analysis of Fe3C by Lipson and etch.' However, it was impossible to determine whether iron and manganese atoms occupied ordered positions because of the small difference between the atomic scattering factors of iron and manganese. The atomic positions in Mn5Cz (Refs. 8 and 9) and Fe5C2 (Refs. 7 and 8) have been obtained only by comparisons made with the isostructural compounds P~SB~.' Since X-ray diffraction techniques were used in these investigations, accurate positioning of the carbon atoms, which have a low atomic scattering factor, was difficult. No attempt has been made to determine the atomic positions in the other carbides previously studied. It was felt that an investigation of the lattice parameters of a number of intermediate carbides of the types (Fe,Mn)sCZ and (Fe,Mn)& would be of interest. It seemed likely that a neutron-diffract ion study of such carbides would indicate whether ordering occurred between the iron and manganese atoms because of the large difference between the neutron-scattering cross sections of iron and manganese. It also seemed probable that such an investigation would provide a determination of the atomic coordinates of the carbon atoms. I) EXPERIMENTAL DETAILS Specimens, each weighing approximately 20 g, were carefully prepared according to the following proportions: The components were 500-mesh powders of 99.995 pct purity iron and spectroscopically pure carbon and a 200-mesh powder of 99.995 pct purity manganese. The component powders were intimately mixed by prolonged shaking, then each specimen was inserted into a spot-welded cylindrical container of tantalum foil, whose end was closed but not sealed. Each specimen in its envelope was then sintered at 1050° C for 24 hr in a thin-walled evacuated quartz capsule, such a time having been previously found sufficient for equilibrium to be attained.' Each specimen was then quenched in order to attempt to retain the high-temperature phase, as the literature indicates that transformations may occur on cooling. Debye-Scherrer X-ray photographs were taken of each specimen using a 114.6-mm-diam camera, Fig. 1, patterns 2 to 6. The exposure time was 6 hr using filtered iron radiation at a tube voltage of 40 kv and a tube current of 12 ma.

Jan 1, 1967

By G. A. Moore, D. W. Williams, C. E. Sims

During the past several years the steel casting industry has made studies of heavy castings in which the test bar has been taken from heavy sections rather than from attached or separately cast coupons. It has been noted that the ductility properties of these heavy sections are often lower than those normally expected. Such lowered ductility is usually accompanied by a spotty test bar fracture and the ductility values often can be greatly improved if a low-temperature aging treatment is given to the casting. A loss of ductility of this type is considered "abnormal," since it is not accompanied by an increase of tensile strength or hardness, and "temporary" when the ductility can be restored by aging, The cure of such an abnormal condition represents a real improvement in the quality of the steel. Some hundreds of previous investigations, largely qualitative in nature, have established beyond reasonable doubt that hydrogen is normally present in newly manufactured steel and that this gas, in small amounts, can cause a temporary ab- normal loss of ductility. The commonly observed association of high gas content and low ductility has given strong evidence for the presumption that hydrogen, possibly assisted by other gases, is the primary cause of the low ductility observed. Accordingly, the Steel Founders' Society of America has, since Nov. I, 1944, sponsored investigations at Battelle Memorial Institute whose primary objective is to obtain quantitative information on the relation of the amount of hydrogen and nitrogen in steel, together with associated methods of steelmaking and treatment, to low-ductility effects and porosity. In order that these investigations might proceed on a quantitative basis, hydrogen analyses of a precision considerably higher than any previously reported in the literature were necessary. 'The method chosen was selected entirely on the basis that it had the highest probability of freedom from uncontrollable errors and will be described in detail in another publication.' Briefly, the method used consisted of the hot extraction of solid pieces of steel weighing from 45 to 50 g in a highly evacuated quartz tube maintained at 1050°C (1925°F) for a period of approximately 40 hr. The greatest precautions were taken to eliminate blanks and insure a sound gas-collection system. vacuum and temperature conditions were maintained automatically. Mercury-filled risers were used for the introduction of samples in order that the System could be degassed thoroughly in

Jan 1, 1949

By C. E. Sims, G. A. Moore, D. W. Williams

During the past several years the steel casting industry has made studies of heavy castings in which the test bar has been taken from heavy sections rather than from attached or separately cast coupons. It has been noted that the ductility properties of these heavy sections are often lower than those normally expected. Such lowered ductility is usually accompanied by a spotty test bar fracture and the ductility values often can be greatly improved if a low-temperature aging treatment is given to the casting. A loss of ductility of this type is considered "abnormal," since it is not accompanied by an increase of tensile strength or hardness, and "temporary" when the ductility can be restored by aging, The cure of such an abnormal condition represents a real improvement in the quality of the steel. Some hundreds of previous investigations, largely qualitative in nature, have established beyond reasonable doubt that hydrogen is normally present in newly manufactured steel and that this gas, in small amounts, can cause a temporary ab- normal loss of ductility. The commonly observed association of high gas content and low ductility has given strong evidence for the presumption that hydrogen, possibly assisted by other gases, is the primary cause of the low ductility observed. Accordingly, the Steel Founders' Society of America has, since Nov. I, 1944, sponsored investigations at Battelle Memorial Institute whose primary objective is to obtain quantitative information on the relation of the amount of hydrogen and nitrogen in steel, together with associated methods of steelmaking and treatment, to low-ductility effects and porosity. In order that these investigations might proceed on a quantitative basis, hydrogen analyses of a precision considerably higher than any previously reported in the literature were necessary. 'The method chosen was selected entirely on the basis that it had the highest probability of freedom from uncontrollable errors and will be described in detail in another publication.' Briefly, the method used consisted of the hot extraction of solid pieces of steel weighing from 45 to 50 g in a highly evacuated quartz tube maintained at 1050°C (1925°F) for a period of approximately 40 hr. The greatest precautions were taken to eliminate blanks and insure a sound gas-collection system. vacuum and temperature conditions were maintained automatically. Mercury-filled risers were used for the introduction of samples in order that the System could be degassed thoroughly in

Jan 1, 1949