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By R. K. Iyengar, G. C. Duderstadt

An investigation was carried out to determine the effect of Ca-Si additions on the dissolved oxygen content of liquid steel. An apparent equilibrium was reached after holding the melt for some time when the total oxygen content of the melt was identical with the dissolved oxygen. Results of the investigation show that for deoxidation with silicon and manganese the apparent equilibrium is reached after 8 to 12 min and the oxygen content of the melt is in good agreement with values reported in the literature for similar steel compositions. Ca-Si additions decrease the dissolved oxygen content appreciably below that obtained with Si-Mn deoxidation. It is postulated that some calcium dissolved in liquid steel at the time of its vaporization combines with dissolved oxygen to form CaO which then fluxes the manganese silicate, thereby lowering the activity of the deoxidation products. Slow flotation of calcium silicate inclusions is attributed to their slower growth rate. An addition of aluminum (to yield <0.005 pct Alsol) prior to introduction of Ca-Si improves the kinetics of removal of resulting deoxidation products. WITH the introduction of continuous casting of billets and blooms, application of calcium-containing alloys for deoxidation purposes has gained new interest. More so than in conventional ingot casting, the degree of control of the dissolved and total oxygen contents in steel for continuous casting can determine the success or failure of the operation because these affect both surface (pinholes) and internal quality of the billets. Of the available deoxidizers, only silicon has so far found wide application. However, in the typical range of application (0.20/0.30 pct Si), it is too weak a deoxidizer to suppress pinhole frequency to the level desirable for all but the least demanding appli-cations (approximately 10/50 pinholes per sq ft, de-pending on degree of subsequent reduction). On the other hand, Vincent&apos; has shown that it requires ap-proximately 0.007/0.008 pct A1 soluble in the steel to suppress pinhole formation to <10 pinholes per sq ft. In view of the difficulty of consistently maintaining this aluminum level and the associated problem of tundish nozzle constriction2 when aluminum is added to the ladle, steelmakers have searched for other de-oxidation alloys to circumvent the problem. Calcium-containing alloys offer such a possibility. When employed as a partial substitute for silicon, CaSi (30 pct Ca/60 pct Si) additions are reported to yield adequate pinhole contro1.3 Its use simultaneously preserves the "fluidity" of the steel and ensures good castability.4 Oxygen contents as low as 0.007 to 0.014 pct have been obtained with CaSi additions varying between 3 to 8 lb per ton.5-7 Due to the high degree of vaporization of calcium at the temperature of molten steel and the different methods used to introduce it into the liquid, the reported results show considerable scatter and lack of consistency. According to several investiga- deoxidation tors, the flotation characteristics of CaSi products are not as favorable as those found for alumi-num but are similar to those established for silicates with low alumina content.678 Thus, cleanliness ratings were improved when CaSi was replaced by a com-bination of Si + A1 followed by CaMnSi additions.5,9 In view of the lack of a comprehensive description of the deoxidation potential of CaSi alloys, a study was undertaken of the effect of CaSi additions on oxygen content in comparison to Si + Mn and Si + Mn + Al. The alloy chosen for this study contained 63 pct Si, 32 pct Ca, <3 pct Al, and 2.5 pct Fe. EXPERIMENTAL PROCEDURE The experiments were divided in three groups as shown in Table I. In each group, the CaSi addition was increased successively while maintaining the melt composition constant. The experiments in the third group were designed to determine the effect of prede-oxidation with small amounts of aluminum. Ingot iron, containing 0.02 to 0.03 pct C and 0.03 to 0.05 pct Mn, was melted in a 100-lb magnesia crucible. Pig iron was added to the melt under air in an induction furnace to attain the desired carbon content of 0.05 to 0.15 pct and thereby control the initial oxygen content of the melt between 0.04 and 0.015 pct. After removal of the slag, the furnace was sealed and argon was introduced through an opening in the graphite cover, Fig. 1. When the desired temperature was reached, electrolytic manganese was added to the melt and pin samples were taken (7 mm silica tubing) to establish initial oxygen content. To obtain maximum efficiency, CaSi and metallic silicon were introduced in a sealed steel pipe into the bath. This procedure assured minimum loss of calcium through vaporization as the deoxidants were always released at the bottom of the melt. Samples were taken at regular intervals and quenched in water. Temperature of the bath was measured with a Pt/Pt-10 pct Rh thermocouple. Portions of the pin sample were used for oxygen analysis; five determinations per sample were made to obtain average oxygen content. Oxygen analyses were made by the inert carrier gas fusion method with frequent cross checks with the vacuum fusion method.

Jan 1, 1970

By J. W. Graham

For many years the author has been cognizant of the difficulty encountered by some in treating with the water influx formulas for unsteady-state fluid flow as pertain to the material balance equation. This has particularly applied in establishing reservoir performance and identifying reservoir pressure, which to the practicing engineer has entailed a trial-and-error procedure, and for others has necessitated resorting to computing devices and reiteration processes. In retrospect this difficulty stems from the fact that reservoir pressure in the material balance formulas, as well as associated with the water influx equations, is an inexplicit term, and the work reported in the past is irrefutable. However, what will be presented in this paper is another approach to the problem, whereby the entire material balance equation will be treated by the Laplace transformation, and reservoir pressure which hereto has been inexplicit, can now be isolated by mathematical procedure to relate that parameter with all the factors contributing to its change. This is the simplification entailed, that treats first with an undersaturated oil reservoir as an integrated effect from the inception of production. The second phase pertains to saturated oil reservoirs that encompass a survey traverse. Although both methods of approach are necessarily different in aspect, the most interesting fact is that the mathematics so deduced are identical. Both the linear and radial water-drive systems are incorporated. for which an illustrated factual example is offered for the latter, treating with a saturated oil reservoir. INTRODUCTIO N What is performed in this work is the simplification of an involved computation by advanced analysis. Although such may be construed as a contradiction when one treats with higher mathematics; nevertheless, when direction is given to such an undertaking the results car. be most revealing. Likewise, it is to be mentioned that the bases for these mathematics have been developed on the expediency of the occasion. This is not to be inferred as a qualification of this work, but rather the demands frequently placed upon the author in his private prac- tice in meeting a time limit. A situation, instead of being fraught with hazards, often has given emphasis to creative thought. What will be entailed in this work is the simplification of the material balance formulas by the Laplace Transformation., Although this reveals entirely new horizons that will be given expression in a forthcoming tract, it suffices in the present instance to limit our attention to this phase of the development that treats both with an undersaturated and saturated oil reservoir. To orient the reader&apos;s thoughts as to what is involved in this simplification is the recognition that reservoir pressure, as such, is an inexplicit term in the material balance equation. This is the independent parameter that defines the total history of performance in the author&apos;s&apos; unsteady-state water influx formulas, as well as the basis for the physical dependency of fluid behavior within the formation as prescribed in the Schil-thuis&apos; material balance equation. Therefore, to isolate reservoir pressure, which is the most essential factor in any reservoir study, is rather a cumbersome procedure entailing either a trial-and-error calculation for the engineer; or as some prefer, a reiteration process performed on a computing device. However, once such an equation can be transcribed as a Laplace transformation, this inexplicitness so expressed can be alleviated to identify reservoir pressure as an explicit function of all the factors contributing to its change. This is the simplification encompassed, that will treat first with an undersaturated oil reservoir as an integrated effect from the inception of production, and secondly, with a saturated oil reservoir as a survey traverse. Although the two approaches are necessarily different because of the uhvsics involved. it is an interesting commentary that the mathematics are identical, showing the interdependency of the two methods. In order to acquaint the reader with this development, the simplest case will be treated first; namely, an under-saturated oil reservoir subject to a linear water drive. However, what may be construed for this example as an idealistic case is actually a most practical application in certain parts of the world, where the size of the fields are so large that radial water-drive approaches the configuration of a linear drive. Further, to avoid the repetition of much symbolism, frequent references will be made to the work of the author and an associate on Laplace Transformations3,

By J. Murray Riddell, Arthur E. Anderson, Grover J. Holt

OUT of the depths of each business cycle we emerge with a stimulus for greater efficiency and a realization of progress in industrial technique. The recent years have not been an exception to this rule, and in retrospect we sense that significant advances have been made in mining practices on the Mesabi Range, with emphasis on speed of production and economy of operation. A survey of such changes does not reveal anything that is fundamentally or basically new, but it is apparent that ideas and machines that have found wide application in industry elsewhere, with necessary modifications, are being put to productive use in mining iron ore. Innovations in transporting and conveying ore from the open pits stand out with greatest prominence, so that, in the main, it will be with these features that this paper will treat, in the review of progress made to this date. The late years have witnessed the development of small deposits for open-pit operation, the cleaning up of pits nearing exhaustion, and in two large operations the approach to the limit for haulage by steam locomotives, owing to grades, making it necessary to recover the ore in slopes, track benches and below the power-shovel limit by a milling and scram operation. For several years small standard-type dump trucks have been used in clean-up or scram operations within the pits, but during the seasor1 of 1936 the first effort was made to use heavy truck haulage in the transportation of stripping and iron ore. The new units in use today vary from 15 to 20 tons in capacity, and are equipped with powerful gasoline or Diesel engines and supplemented by trailers or wagons on rubber or crawler treads. The Diesel engine finds favor with most operators because of fuel economy. These units develop upward of 125 hp. in the 15-ton trucks. The speed of these trucks varies from 2 miles per hour in low gear to 35 in high gear. The transmission affords 12 speeds forward and 3 speeds in reverse.

Jan 1, 1938

By Leon Eliel

TEN years ago .a broad knowledge of aerial mapping, coupled with a smattering of geology, qualified one to speak on the subject of the appli-cation of aerial mapping to geology. Today, with aerial maps a common tool in the hands of expert geologists on every continent throughout the world, it would be nothing short of presumptuous for the author of this paper, who is not a geologist, to give any geological statements on his own authority. Relatively, today we are only purveyors of general geological gossip, with a definite case here and there by way of illustration. But we can present a story of the really marvellous strides that have been made in the evolution of aerial mapping, built around a skeleton of geological tidbits, from which some useful conclusions may be drawn. The average geologist goes about reading his aerial maps much as one would approach the problem of deciphering a cryptogram. To begin with, typical key expressions appear in recurring sequences and under certain conditions. If once the meaning of these. isolated bits of infor-mation can be ascertained, the message begins to take meaning.. In a similar fashion, the geologist works out his key from aerial maps of territory with which he has some familiarity. He learns that a certain type of thin, white line may mean a vein of quartz. He sees that a certain change in the photographic tone of vegetation on the ground reflects two kinds of soils on opposite sides of a contact. He sees that a certain type of alignment of topographical features often means a fault. He learns that by the erosion pattern he can frequently distinguish soft formations from harder ones. And so, bit by bit, he ties together the information of the picture with his experience on the ground until he develops a reasonably creditable capacity of interpretation. Through the complete gamut of surface conditions, ranging all the way from flat, arid, exposed desert terrain to dense jungle, or rugged mountains, the evidence from which the geologist must make his inter-pretation varies with bewildering profusion. The quality of photographs which are obtainable may range from perfect pictures in the desert to almost useless smudges in the steaming jungles. One thing he has learned with certainty-the airplane carrying its mapping camera is a superb reconnaissance tool, only awaiting his ingenuity in correlating the pictures with the ground to simplify most exploratory problems.

Jan 1, 1936

By Gareth Thomas

The analysis of Kikuchi pattersns of exct ovientalions from single cryslals and paired Kikuchi lines from single and overlapping crystals is shown to be useful and quanlitalve and is applied to Phase transfovnzcitions including ordering, spinodals, mavten-silic, and nuclealion and growth pyocesses. 112 pinciple, the analysis of exacl orientations enables the crystal system and the Bravais lattice of a crystal to he determined. The advantages of the davk-field imaging technigure for detecting vevy small precipitates are also described. ALTHOUGH Kikuchi electron-diffraction patterns were first observed nearly 40 years ago,&apos; little systematic application seems to have been made of them, until fairly recently during electron microscopy, when their usefulness in contrast experimen and for determining exact orientations8&apos;9 has been pointed out. With the availability of gonio-metric specimen tilting stages it has now become possible to make much wider use of diffraction patterns, particularly the Kikuchi pattern, which is the main subject of this paper. The treatment presented here is not exhaustive but it is hoped that it will stimulate more use of Kikuchi patterns during electron-microscopy investigations. The Kikuchi pattern is formed as a result of Bragg diffraction of the inelastically scattered electrons produced during the interaction of the beam and thick specimens, The important feature of these patterns is that they give an accurate representation of the symmetry of the crystal being investigated, so that it is possible to identify crystal systems and even the Bravais lattice. This means that new structures, e.g., formed in phase transformations, may be identified during normal electron microscopy, so that Kikuchi-pattern analyses considerably extend the uses of the electron microscope. Recent work has also shown that dark-field images are more informative than bright-field images, particularly, for observing small precipitates. The second part of this paper discusses some applications and advantages of dark-field imaging in studies of two-phase systems. 1) DIFFRACTION PATTERNS 1.1) Spot Patterns. Electron-diffraction spot patterns have their limitations because of the importance of the form factor on the intensities and shape of the reciprocal lattice points. Because of the extension of these points into relrods, reflections are possible over a large angular range (+5 deg) and the patterns from thin regions can be complicated because second-layer relrods intersect the reflecting sphere. Spot patterns can thus give only an approximate idea of the crystallography unless the foil is tilted into exact orientation. In this case the spot pattern is symmetrical, with equal numbers of spots on the positive and negative zone directions about the origin. Such cases are necessary for structural analyses and have been used recently to determine the crystal structure of the ordered Ta64C phase." Exact orientation means that the plane of the reciprocal lattice lies exactly normal to the incident beam as shown in Fig. 1(b). It should be noted that in exact orientations the angle of reflection is less than the exact Bragg angle 9 so that the reciprocal lattice points lie to the outside of the sphere, Fig. 1(b). This deviation is denoted by the parameter s and in the usual convention4 s is negative for exact orientations and, of course, zero at the exact reflecting position shown in Fig. l(a). In order to avoid secondary reflections from thickness relrods it is advantageous to work in thicker regions of foils. Diffraction from thick regions may also produce Kikuchi patterns and as dis-

Jan 1, 1965

By Billy L. Crowder, John M. Fairfield

The implantation of B+ , P+, and As&apos; into silicon has been studied with the purpose of making shallow p-n junctions. The influence of such parameters as 1) ion energy, 2) target orientation and temperature, 3) total dose, and 4) annealing schedule was investigated. An energy range of 70 to 300 kev was used for boron and phosphorus implants and up to 500 kev for arsenic. It is found that the experimental projected range agrees well with theory and that shallow junction depths can be made reproducibly. ION implantation has received much attention recently as a technique for doping semiconductors. Specifically, it has the potential of supplementing or replacing the diffusion process as a method for making p-n junctions. In a few specific cases it has been used successfully to make semiconductor junction devices. Potential advantages of ion implantation doping over diffusion techniques are: 1) It affords greater control of shallow junction depths (< 0.2 µ) while maintaining high peak concentrations. This is particularly important for high-speed switching devices, since lower junction capacitances and resistances can be achieved. 2) More precise registration of small planar structures can be realized if proper masking procedures are employed. This advantage is especially useful in the design of high-density integrated circuits. It has been used to advantage in FET fabrication since the edge of the source or drain can be aligned precisely at the edge of the gate electrode.&apos; 3) Ion implanatation permits lower temperatures than diffusion techniques. This factor alleviates the problem of compatibility of diffusivities often encountered when designing multiple-junction structures. Also, the lower temperatures create fewer thermal defects and dislocations, which may account for the high efficiency of some ion-implanted solar cells.2 4) Impurity profiles can be more easily tailored to resemble ideal distributions. Successful exploitation of the potential advantages of ion implantation techniques will depend on increased knowledge and understanding of the subject. The factors likely to be influential in determining impurity distribution profiles in ion-implanted single-crystal targets have been reviewed by J. F. Gibbons.3 In addition to the mass and energy of the implanted ion, the total dose, target orientation, and target temperature are important parameters. The annealing temperature required for removing lattice damage and incorporating the implanted species on an electrically active site is very important. This paper describes an investigation of some of these factors. Implants of boron, phosphorus, and arsenic into silicon have been studied. Energy ranges of 50 to 300 kev were used for boron and phosphorus and up to 500 kev for arsenic. In addition to the implantation energy, the effects of total dose, target temperature, and post implant anneal have been investigated. EXPERIMENTAL PROCEDURE The implantation targets were silicon wafers cut from Czochralski-grown crystals, lapped, and chemically polished. The orientations were (111), (110). and (100) with misorientations of up to 7 deg from the principal axis. For this study, accurate target alignment (i.e., within 0.1 deg) was not available and quoted misorientation values should be regarded as approximate . The implantation equipment consisted of an ion source, a 300-kev linear accelerator tube, an electromagnetic separator, and the associated target supporting and beam focusing assemblies. The ion source was a simple oscillating electron type source,4 which has been described elsewhere.5 The gaseous compounds BF3, PF5, and AsH3 were used as ion sources for B+, P+, As+, and AS+&apos;. Analyzed current levels of up to 20 pamp could be obtained; however, for this investigation target current levels of 1-3 µ amp were usually employed. The analyzed ion beam was collimated through a double slit (1.4 x 0.4 cm) and swept perpendicularly to the long axis of the slit such that an area of about 2 sq cm on each target was covered. Dosages of around 1015 cm-2 were normally employed, but smaller amounts were also used for comparison. A uniform flux density over the bombarded area was assured by the continuous use of profile monitors similar to those described by Wegner and Feigenbaum.6 Post-implant annealing was accomplished in an argon atmosphere in a temperature range of 600" to 950°C. It was not part of the purpose of this investigation to study the annealing kinetics; however, some isochronal and isothermal anneal experiments were conducted to determine the time and temperature necessary to render a reasonably high portion of the implanted ions electrically active (i.e., higher than 50 pct). Post-implant anneal temperatures of around 900° and 600°C were required for boron, and arsenic and phosphorus implants, respectively. Arsenic and phosphorus implants increased in conductivity rather abruptly at the proper anneal temperature of the isochronal curve, but boron increased more gradually over a wider range. Isothermal anneal curves were reasonably flat after 10 min, so an anneal time of 1/2 hr was used for the experimental results described below. The profiling techniques were: 1) neutron activation analysis, 2) differential sheet resistance,7 and 3) junction staining.8 The differential sheet resistance technique is commonly employed in this type of study. Its principal disadvantage is the uncertainty of the ef-

Jan 1, 1970

By R. K. Ham, M. L. Wayman

TD-Nickel has been broken in tension and in fatigue at voom temperature. Rod specimens failed in tension by necking, with axial cracks attributed to voids elongated in the extrusion direction. Fatigue specimens failed in shear. Thin-film electron microscopy showed that the subgrain structure of TD-Nickel was very stable, and that particle-matrix detachment was very difficult, in tension and fatigue. TD-Nickel softened slightly during fatigue but had a high fatigue ratio (0.5at 10&apos; cycles). Fractography suggested that Stage I fatigue crack propagation is greatly extended in TD-Nickel. Td-NICKEL* is a dispersion of 2 pct by volume of thoria (ThO2) in nickel, produced by powder-metallurgical methods including compaction, sintering, and extrusion. The spherical thoria particles, which may have a mean diameter of a few hundred angstroms, are dispersed with a mean planar spacing of a few thousand angstroms. By a combination of cold working and annealing, a subgrain or cell structure of dislocations intimately associated with the dispersion can be produced.&apos; This gives the material useful tensile properties which are extremely resistant to exposure to high temperatures.&apos;-= At the same time, the material shows considerable ductility.3&apos;4 At the beginning of the present work, it was considered of great interest to investigate the mechanical stability of TD-Nickel under conditions of fatigue. On the one hand, materials which derive strength from a cold-worked structure are unstable in that they are susceptible to fatigue softening: in addition, the presence of discontinuities such as the particle-matrix interfaces might be expected to assist in the initiation and propagation of fatigue cracks, in that they may provide local concentrations of internal stress and sites for the initiation of voids." On the other hand, the substantial ductility of TD-Nickel suggests that if it obeys Coffin&apos;s relation8 (or the more refined form proposed by Manson9) it should have good fatigue resistance. The initial purpose of this investigation was to assess the importance of these factors. Also, relatively little fundamental work has been done on the mechanism of fatigue in dispersion-strengthened materials. Work on overaged A1-4 pct CU10-12 revealed a very large Bauschinger effect indicative of internal stresses at the particles, and very great fatigue hardening1&apos; presumably due to the multiple slip stimulated by these internal stresses, followed by softening which was initially due to softening in the matrix, but later might have arisen from cracking at the particle-matrix interfaces. The study of overaged Al-4 pct Cu could not settle this latter point by the electron microscopy of thin films, since the dispersion is too coarse. A previous study of the fatigue of internally oxidized copper13 was complicated by inter granular failure, attributed to oxide particles at grain bouhdaries; internal oxidation of single crystals, however, improved their fatigue properties.&apos;3 Investigations of SAP (sintered aluminum powder) are complicated by the complex particle shapes, and the possibility of continuous internal oxide films.14 It was hoped to avoid these difficulties with TD-Nickel, which had the further advantages that it was commercially available and suitable for study by the thin-film technique. 1) MATERIALS AND EXPERIMENTAL PROCEDURE TD-Nickel was purchased from the Driver-Harris Co. as 3/9-in.-diam rod which had been extruded, swaged, and "stress-relieved" (normally at 1010°C for 1 hr). Continuous-radius fatigue specimens with a minimum diameter of -0.1 in. were ground to shape and electropolished in 40 pct phosphoric, 35 pct sul-furic, 25 pct water at 25oC, with a stainless-steel cathode, at -6 v. Fatigue tests were carried out at room temperature with a Sonntag SF-1-U machine operating in push-pull at 1800 cycles per min, and in an Instron TT-C-L modified for reversed stressing at 26 cycles per min as described elsewhere.10 Round tensile specimens were ground with 0.85-in. gage lengths of 0.135 in, diam, electropolished, and tested in a Tinius Olsen hydraulic machine. The surfaces of fatigue specimens were examined with a Reichert metallograph. Discs for electron microscopy with a Siemens Elmiskop I were spark-cut 0.01 in. thick with a modified Servomet 11 employing a tool of moving molybdenum wire, cleaned in 50 pct acetic, 30 pct nitric, 10 pct phosphoric, and 10pctsul-furic at 85oC, and thinned by the window method in the electropolishing solution at -20°C and -6 v. Two-stage replicas (parlodion, then Pt-50 pct C self-shadowed at 40 deg) were taken from fatigue fracture surfaces for electron microscopy. Plane sections parallel to the specimen axis and containing the direction of fatigue crack propagation were polished, etched with Carapella&apos;s reagent, and examined optically. Transmission Laue X-ray photographs of as-received material electropolished to a point were used to determine preferred orientation. 2) RESULTS 2.1) The Structure of As-Received Material. Grains -1 µ diam and elongated 20 to 30 u in the direction of the rod axis were observed, With&apos; elongated "intergran-ular" voids (-4 p diam and -90 µ long and identified as such using longitudinal and transverse sections and

Jan 1, 1968

By J. L. Lamon, W. Crafts

Study with the electron microscope of the carbides in vanadium-chromium-molybdenum steels after tempering up to 1000 hr at 600 teelsto 1400°F confirmed that alloy carbides are formed at the secondary hardening temperature by decomposition of the plate-like iron carbides. It was also demonstrated that vanadium carbide persists as much smaller particles than do chromium- or molybdenum-bearing carbides. Conditions conducive to the formation of fine vanadium carbides are indicated to be favorable for high temperature strength. IN order to determine the effects of long exposure at high temperatures on vanadium-bearing steels, a survey has been made of their hardness and carbide structure. The behavior of carbides in the tempering of martensite was studied by X ray diffraction and electron microscope examination of electrolytically extracted residues in greater detail than in an earlier investigation.&apos; A group of steels with about 0.25 pct carbon and containing chromium up to 5 pct, molybdenum up to 1 pct, and vanadium up to 1 pct was either quenched or annealed and then tempered for peri- ods of up to 1000 hr at 600° to 1400°F. Their hardness after tempering agreed with the Hollomon and Jaffe2 relation of equivalency of time and temperature, and with the degree of secondary hardening predicted from composition. Further, the appearance of the carbides indicated that the time and temperature equivalency relation was also applicable to the degree of carbide development. The mechanism of the tempering of martensite was demonstrated more clearly than in the earlier study. It was confirmed that carbides develop from martensite as poorly defined plates of the Fe2C type carbide followed by thickening of the plates with a transition to Fe,C. Finally the plate structure deteriorates into a lacy mass from which alloy carbides emerge as chunky particles that grow slowly with further increase of tempering temperature. Vanadium carbide derived from tempered martensite was found in characteristically small particles that tended to grow very slowly. The addition of chromium or molybdenum to a steel with predominant vanadium carbide tended to introduce carbides of a chromium- or molybdenum-bearing type having a somewhat larger particle size. The Cr,C, type carbide particles were larger than those of the V,C, type and somewhat smaller than the carbides in steel containing both Cr,C and M,C. Similar observations were made of the carbides in the pear lite of annealed steels. It appeared that high temperature properties would be benefited by the retention of the fine carbide particles that result from a balance of composition and heat-treatment designed to produce a maximum amount of vanadium carbide. Procedure: The steels used in the investigation were made with a base of Armco iron in a high-frequency furnace at the Union Carbide and Carbon Research Labs., Inc. The steels were deoxidized

Jan 1, 1951

By P. Greenfield, C. C. Smith, A. M. Taylor

The Mg-Zr alloy ZA and Mg-Mn alloy AM503(S) are shown to have a markedly improved resistance to creep deformation after suitable heat treatments. This improvement makes them suitable for certain stress-bearing fuel element components in nuclear reactors. The extent of strengthening is described and an explanation of the behavior of both materials is given, based on a combination of strain-aging and grain growth. The increase in operating temperatures of fuel element components in Calder Hall type nuclear reactors has necessitated the development of magnesium base alloys with a very high resistance to creep at temperatures up to 500°C. Such alloys are not required for fuel element cans, which require high-creep ductility rather than strength, but for can supporting and stabilizing components, which are needed to support the imposed loads without deforming more than about 1 pct in times of up to 40,000 hr. The amount and type of alloying addition made to magnesium for these parts is limited by the necessity of keeping the cross-section to thermal neutrons as low as possible. The alloys must also possess a high resistance to oxidation in CO2. Alloys which have been developed for this application include ZA, an alloy of magnesium with 0.5 to 0.7 pct Zr and AM503(S), an alloy of magnesium with 0.5 to 0.75 pct Mn. In the as-extruded condition these alloys are very weak and ductile in creep but it has been found that they can be strengthened to a significant extent by heat treatment. This paper describes the method of developing a high-creep resistance in ZA and AM503(S), the extent of the strengthening produced and discusses the probable mechanisms of strengthening. TEST MATERIALS Specimens were taken from typical casts of ZA and AM503(S) alloys extruded into 2 1/4-in.-diam bars, supplied by Magnesium Elektron Ltd. Typical analyses of the bars were as follows: The as-extruded mean grain diameter was 0.001 to 0.002 in. for the ZA alloy and 0.003 in. for the AM503(S) alloy. EXPERIMENTAL METHODS Extruded bars of ZA alloy, 2 1/4 in. in diameter and 9 in. long, were heat treated in electrical resistance furnaces in an atmosphere of flowing CO2 containing 50 to 300 ppm water, thereby reducing the extent of oxidation compared with that which would have occurred in air. Heat treatments were carried out at 600oc for times of 8, 24, 48, 72, and 96 hr and material was subsequently both furnace cooled and water quenched. In order to measure the effect of time of heat treatment, specimens were creep tested at 400°C and 336 psi for about 1000 hr. Subsequently, the behavior of material heat treated for 96 hr at 600°C and furnace cooled was tested at a variety of stresses from 200° to 500°C. Tests were also conducted at 200o and 400°C on material in the as-extruded condition for comparative purposes. With the AM503(S) alloy, only the effect of heat treatment at 565°C for 4 hr was examined. It has been shown1 that such a heat treatment produces marked strengthening in this alloy. Tests on this material were conducted at a variety of stresses at 200°, 300°, and 400oc with comparative tests on as-extruded material at 200o and 400°C. The creep tests were carried out on machines using dead-weight loading and direct micrometer strain measurements on specimens 5 in. long and 0.357 in. diameter. At temperatures of 400° C and below, the creep tests were conducted in air, but at higher temperatures an atmosphere of CO2 was used. Grain size measurements were made on ZA in the extruded and heat treated states and on each specimen after creep testing. This was done by a line count of a minimum of 20 grains in two or three random fields in the longitudinal and transverse directions. The same method was used for measuring the grain size of as-extruded AM503(S), but the grain size of the heat treated material was so large that this method could not be employed. For heat-treated AM503(S) the large grained characteristics (between 0.1 and 1 in.) were confirmed by the measurement of individual grains. In the case of the ZA alloy, specimens taken from various stages in the program were analysed for hydrogen by a combustion method. Material in various states was also analysed for the soluble and insoluble zirconium content by dissolving in dilute hydrochloric acid. This technique has been useda for the determination of amounts of zirconium present

Jan 1, 1962

By H. Rumfelt

The author demonstrates an approach for analyzing overcasting requirements for a stripping project. This approach to the problem employs indicated trends in the relationship of the weight of the machine (only electropowered draglines are considered) to its ability to do stripping work. Strip mining in the domestic coal industry is contributing a greater proportion of overall production than at any time in the past. U.S. Bureau of Mines statistics show that the percentage of total production mined in 1958 by stripping methods increased to more than 30 pct, up from 22 pct in 1951. The tendency to favor strip and open pit mining exists in other mining activities, but such trends are not as clearly outlined as in the coal industry. Significantly, the depth of overburden in coal properties considered suitable for stripping is also increasing. A depth of 50 to 60 ft of overburden was once considered to be about the maximum amount that could be handled economically. Today, a depth of 80 to 100 ft is frequently taken into consideration for simple overcasting operations (i.e., excavating overburden and dumping it in the spoil position where it remains indefinitely). Accompanying these changes, there have been continuing studies searching for procedures to appraise deeper stripping problems. Although the only known practicable way to accurately evaluate a proposed stripping venture is to make studies (including cost estimates) step by step, it is nevertheless desirable to have a quick method for making preliminary evaluations of potential strip mining operations. A recently devised digital computer method of providing a preliminary simple overcasting analysis for a stripping prospect relates the indicated trends in the relationship of the weight of the machine to its ability to do stripping work. In addition, this approach employs situations where the geometry of each cut-and-spoil section is assumed to take certain defined relationships for varying overburden depths. Slopes are necessarily considered to be stable, which means such practical factors as the mechanics of soils are neglected for the sake of convenience. Definition of Terms: Photographs A and B show a shovel-type and a dragline-type of simple overcast operation, plus terms used to denote certain parts of a pit. Pits that follow a straight line when projected on a horizontal plane are referred to as straightaway. It has been assumed that all section drawings accompanying this article pertain to straightaway cuts which, in turn, means that areas can be compared by relative volume. The volume of overburden is measured in virgin cubic yards. Material displaced from its virgin state to a spoil area normally occupies a larger volume than when in situ; the difference is termed swell, and it is expressed as a percentage of the original volume. For example, if the original cut volume is denoted V cu yd, and the spoil volume is 1.2 V cu yd, the swell is a positive 20 pct. MAXIMUM USEFULNESS FACTOR (MUF) CONCEPT Men experienced in overburden removal give emphasis to the weight of the machine in relation to its value as an excavator. From the writer&apos;s understanding, value has been only loosely defined and discussed generally and vaguely. The concept is considered important, however, since it is based upon the observations of many men. It provides a clue for the approach taken to solve deep stripping problems. In the procedure described below, value has been arbitrarily established as the product of the nominal dipper size of the shovel (or dragline) times a functional dumping reach. MUFs—Shovel: A shovel&apos;s capability to handle thick overburden is usually limited by its ability to dispose of the spoil. Thus the dumping reach, as well as its dumping height, is significant. The angle of repose of spoil material must also be considered. Although such slope angles vary among different mines, jobs, and materials, a slope of 1.25 to 1, frequently found in both planning and practice, is used by this author in the illustration of this analytical method. The relationship of the shovel&apos;s geometry to a stripping operation is shown in Fig. 1. To gain maximum advantage in constructing spoil piles, the shovel is placed so that its tracks adjacent to the spoil are as close as possible to the rib of the coal deposit. A vertical plane passing through the line

Jan 1, 1961

By G. P. Airey, R. F. Mehl, T. A. Hughes

The coarsening of cementite particles in a ferrite matrix has been studied in a series of steels with 0.15 pct C only and 0.15 pct C plus 1 pct Ni, Mn, and Cr, respectively. Two initial states were employed: quenched nartensite, and quenched and cold-rolled martensite. A series of tempering temperatures between 500&apos; and 700" and tempering times of up to 190 hr were used. The structures were studied by replica and transmission electron microscopy. Particle size distribution curves were determined. From the average size value coarsening curves were obtained. These were plotted in accordance with the Wagner analysis assuming diffusion control. A discussion of the significance of the results is given. L HE reactions occuring upon the tempering of martensite have long engaged the attention of metallurgists. The latter stages, when cementite particles coarsen in a ferrite matrix, have been studied both qualitatively and quantitatively. Studies of such coarsening processes have recently been spurred by the publication of the Lifshitz-Wagner theory1, and the extension of this to the a Fe-Fe3C system by Oriani3 and by Li, Blakely, and einold. Following Wagner the coarsening process is often designated as "Ostwald Ripening". The only quantitative data on the rate of coarsening, except for the work of Hyam and uttin,&apos; in the a Fe-Fe3C system are those of Bannyh, Modin, and odin&apos; for a commercial eutectoid steel and those of Heckel and ereorio" using a pure eutectoid steel. The data of Bannyh, Modin, and Modin have been employed by 0riani3 to derive the a Fe-FeE interface energy. The reaction is one of the most important ones in steel and is worthy of detailed study. This is the purpose of the present study. Laboratory heats were prepared; these were steels with approximately 0.15 pct C, selected so that the num ber of carbide particles would be relatively small and thus so that the overlapping diffusion fluxes would be minimized, presumably a desirable circumstance.&apos;-3 In addition to Fe-C alloys, comparable heats containing 1 pct of Ni, Mn, and Cr, respectively, were included with a view of appraising the effect of alloying elements. This report includes an account of the micro-structures observed, primarily with the electron microscope, and of kinetic data and their interpretation. MATERIALS AND TREATMENT The alloys were prepared from electrolytic iron ("Plastiron") and high-purity graphite; these were melted in a zirconia crucible using a vacuum furnace. The alloy steels were made by adding electrolytic nickel, electrolytic manganese, and "vacuum grade" chromium, respectively, under a partial pressure of argon. Each melt was poured into a mold within the vacuum furnace and cooled in the mold. The ingots were 2 in. in diam. and 8 to 10 in. long. The analysis of the alloys is given in Table I. These ingots were hot-rolled to strip 0.1 in. thick, then cold-rolled to 0.05 in. and each alloy split into two batches. One batch was austenitized at 1200 for 1 min, quenched in cold brine, then cold-rolled to 0.02 in.; samples given this treatment are hereinafter designated as "worked". The other batch was cold-rolled to 0.025 in., austenitized at 1200" for 1 min, and quenched in cold brine; such samples are hereinafter designated as "quenched". These two batches were then tempered, as below. The purpose of the treatment given the first batch was to provide an initial structure of cold-worked martensite, with the expectation that the additional defect structure created by cold work would encourage a higher rate of nucleation of cementite on tempering and hence a more uniform distribution of cementite particles. Individual specimens were sealed in evacuated quartz or Pyrex tubes, then tempered in a muffle furnace. The temperature control was better than 3&apos;C at 700. Tempering treatments wer: performed at 400°, 500°, 550°, 600°, 65o°, and 700C for time periods between 15 min and 190 hr. PREPARATION OF SPECIMENS Specimens for optical and replicalelectron microscopy were mounted, polished conventionally, and etched with 2 pct nital. For electron microscopy, single-stage "formvar" replicas were made, dry-stripped and rotary-shadowed with chromium at an angle of 30 deg. Carbide extraction replicas were prepared from electropolished specimens usirig the method described by Smith and uttin.&apos; Thin foils for electron transmission microscopy were prepared by chemical thinning in an H202-HF bath prior to electropolishing in a chromium trioxide-acetic acid solution. The most

Jan 1, 1969

By F. Bonaccorso, G. Venturello, C. Antonione

A study of the effect of small amounts of interstitial impurities on recovery and re crystallization in high-purity iron (99.995 pct) has been undertaken. This paper gives results on the effect of carbon, introduced in small-dosed amounts @om 0.0005 to 0.0086 wt pct) by heating iron specimens of high purity m a static atmosphere of CO + ,. The materials prepared in this way, cold-worked 80 pct and subjected to a series of isochronal and isothermal annealings, were submitted to examinations by X-rays, micrographs, and hardness tests. It was observed that effect of carbon is remarkable in the sense of blocking recovery of mechanical properties up to the temperature at which re crystallization begins. On the contrary, carbon has a negligible effect on primary re crystallization temperature, when compared with the known effect of substitutional impurities. This is in agreement with the high mobility of interstitials. In effect, only a slight decrease, -20 pct, of the grain-boundary motion rate was noted, due to the interaction between the grain boundary and the carbon atoms. On the other hand, in the samples in which the carbon content is above the solubility limit at the temperature at which re crystallization occurs, a slight increase of nucleation frequency is noted due to the presence of precipitated carbides. ThE effect of purity on recovery and recrystalli-zation phenomena has been known for a long time; however, recently, new attention has been given to the problem since new methods for obtaining metals with extremely low impurity contents have become available. Most of this research work essentially concerns the effects of impurities which cause precipitates or give rise to substitutional solid solutions. The works of Bolling and winegard1 and Aust and utter&apos; on lead, and Vandermeer and orddon&apos; on aluminum, 01sen4 on nickel, and Abrahamson and Blakeney on iron should in particular be referred to. On the effect of this type of impurities a quantitative theory has been formulated by Detert and Lucke6 and has lately been discussed critically by Cahn7 and Gordon and vandermeer.&apos; Interstitial solid solutions in iron have not as yet been studied. As the study of the effect of interstitials is of great interest both from a theoretical and practical standpoint, it was deemed useful to examine the effects of carbon, nitrogen, and boron on recovery and primary recrystallization of iron. There already is some work by Chaudron et al.,1-" on the effect of interstitials on iron; their work, however, mainly concerns secondary recrystallization. The present paper refers in particular to the effect of carbon. EXPERIMENTAL PART Preparation of Materials. The pure iron used for this research was obtained from FeCIS recrystal-lized and purified by extraction with isopropylic ether. From the ferric chloride purified in this manner, hydroxide was precipitated with a solution of very pure ammonia, and, by calcination in pure sintered alumina crucibles, oxide was obtained. Reduction of the oxide to iron sponge was performed in sintered alumina tubes with very pure hydrogen at 650°C; at the end of the operation temperature was increased to 900°C. Specimens for the experiments were obtained by sintering the sponge at 1480°C in pure Hz after a pre sinter ing treatment at 900° C. It is important to note that the treatment at 1480°C in Ha produces a further purification from more volatile elements such as zinc, cadmium, arsenic, lead, and tin. Details on the preparation and characteristics of this type of very pure iron are given in a previous work.&apos;&apos; Only the complete analysis performed by neutron-activation methodsz3 is given here, Table I. Some of the specimens prepared in this way were carburized in the 0 region with very low amounts of carbon by treating them at 700°C in a static atmosphere of Ha containing a definite amount of CO. The set-up used is described in Fig. 1. A gas-tight quartz tube containing the specimen to be carburized and an internal friction control specimen, after being evacuated, was filled with Hz

Jan 1, 1963

By H. Groeneveld, C. A. Connally, P. J. Hoenmans, J. J. Justen, W. L. Mason

A miscible displacement pilot using a slug of LPG driven by separator gas was conducted in the Cardiurn reservoir of the Pembina field. The injection pattern was a 10-acre, inverted, isolated five-spot. Upon completion of the LPG-gar phase, an experiment was conducted using a slug of water followed by gas. Calculated performance of the pilot is compared with actual performance. Equations are developed to calculate the distribution of LPG into zones of varying permeability, to estimate the progress of the flood at different times in the various zones and to estimate gas rates after breakthrough. The analysis indicates that permeability stratification was a dominant factor in controlling oil recovery and that oil was completely displaced from the swept pore volume. The results of the pilot indicated that miscible flooding is a practical means of pressure maintenance in this reservoir. The total recovery from the pilot area was good in spite of the early breakthrough of LPG. The effects of stratification were reduced by injecting a slug of water into the partially swept reservoir. INTRODUCTION The Pembina field,&apos; located in Alberta, is the largest oil field in Canada and one of the largest in the North American continent. The reservoir is a stratigraphic trap producing from the Cardium sand. Neither bottom water nor free gas has been found. The recovery of oil by the natural depletion mechanism has been estimated at 12.5 per cent. Pressure maintenance studies of various areas have indicated that the recovery can be increased 21/2 times by water flooding, and a large area of the field is presently under water flood. However, reservoir studies of the North Pembina area indicated that miscible flooding might be competitive with water flooding. A pilot test was conducted to evaluate the performance of a miscible flood. A 10-acre, inverted, isolated, five-spot pattern was selected for the pilot. The pattern area was large enough to minimize wellbore fracturing effects and contained sufficient oil to provide significant working numbers. The performance of each of the four producers could be evaluated individually and compared. In the event of breakthrough in one direction, the effect would be isolated from the other producers. The use of a single injector minimized the volume of LPG required, and, because of the high mobility of gas, one well was sufficient to inject the necessary daily volume to replace the high rate of production. With four producers, the test could be completed in time for results to be evaluated, additional engineering studies to be made and a unit to be formed before the reservoir pressure in the North Pembina area declined below the bubble point. The pilot was located in an area developed on staggered, 80-acre spacing. The injection well was drilled at a regular location, while the four producers were drilled 467-ft north, east, south and west of the injector. Each quadrant and its associated producer were identified according to their direction from the injector— that is, north, east, south or west. The eight surrounding producers on 80-acre spacing were shut in to isolate the pilot area and provide for reservoir pressure observation. The pilot wells were completed using permanent-type completion techniques. After coring, casing was run through the pay section and cemented. Inside 51/2-in. casing, 2 1/2-in. tubing was hung. The wells were perforated opposite the Upper Cardium sand and lightly fractured. Fracturing volumes, rates and pressures were low to minimize the extent of the fractures. The fracturing treatments average 1,000 lb of 20-40 mesh sand in 700 gal of a low fluid-loss sand-carrying agent. Feed rates and wellhead fracturing pressures averaged 5.5 bbl/min at 2,535 psig, respectively. After fracturing, the productivity index was measured in each of the five pilot wells. The average PI of the four producers was 0.41 BOPD/psig drawdown. The measured PI&apos;S were approximately the same as PI&apos;S calculated from core analysis data, indicating that the fracturing treatments were just sufficient to overcome

By N. H. van Lingen

A laboratory stud], has been made to determine what factors affect the penetration rate of roller bits, diamond bits and drag bits in rock drilling with clay /water muds. The rather simple relations that exist when pressures in and around the borehole are equal become more conzplicated when under down-hole conditions the penetration rate is hampered by the existence of a pressure differential between the mud at the hole bottom and the pore liquid at cutting depth. Expressions that have been derived for both the penetration rate and the magnitude of the pressure differential in permeable rock together fully account for operating, rock, mud and bit variables. In impermeable rock a similar pressure differential is caused by the bit action itself. In all cases, the pressure difierential and the reduction in penetration rate increase with the effectiveness of the plastering at the bottom of the hole by mud particles. Where bits are employed whose action is largely that of crushing, however, the plastering may become even more effective owing to the addition of rock particles rubbed into the pores of the rock. With roller bits, a plastically hehaving layer may be formed, which causes a further reduction in penetration. In the case of bits whose action is chiefly scraping, moreover, penetration may be arrested by the bit&apos;s becoming balled-up. The various adverse effects are reduced by thorough scavenging of the hole bottom. This paper shows how with jet bits the efficiency of such scavenging may he improved by suitable choice of the position of the nozzles. INTRODUCTION The reduction in a bit&apos;s penetration rate with increasing depth of hole has been the subject of many investigations. Various investigators &apos;,&apos; have independently reached the conclusion that this reduction occurs not so much because the rock-breaking process becomes more difficult as it does because the lifting of the rock fragments is impaired by a fluid pressure differential holding the fragments down. When such a pressure differential can be avoided, as in air drilling and to a smaller extent in water drilling, penetration rates remain high. Although the range of applicability of these techniques is being extended, most oil wells still have to be drilled with mud. In this paper we present the results of laboratory experiments carried out to determine what factors govern the hold down effect encountered in mud drilling. In the course of this investigation, the well known importance of bottom scavenging came more and more into prominence. Not only may it reduce the magnitude of the hold-down forces, but also it appeared to be a means of preventing the accumulation of a plastic mass of cuttings and mud on the hole bottom and bit which may cause penetration to cease almost completely. So that the effects of fluid pressures may be more readily understood, the factors that govern penetration rate in the absence of these pressures will first be discussed. The effect of down-hole pressures will then be assessed for the case of permeable rock where fluid pressures are well defined, and it will be demonstrated how rock strengthening due to confining can be accounted for. Subsequently, fluid pressures in less-permeable rock will be examined; we will show that in impermeable rock it is the bit action that governs fluid-pressure distribution and hold-down. In the case of poor scavenging and/or high bit load. cutting cake manifests itself. The effect, like various others. appears to depend on the type of bit used. From the very beginning, therefore, we shall base our discussion on the three main types of bits used in rotary oil-well drilling— roller bits, diamond bits and drag bits. Since space is limited, it will be impossible to make more than a passing reference to many aspects of the problem. Moreover. certain relations that are not of primary irnportance to our argument will unavoidably have to be stated in a somewhat dogmatic fashion, and the experimental data on which these are based necessarily must be omitted. EQUIPMENT The drilling experiments were performed on three machines, of which one has been designed for the realistic simulation of down-hole pressure conditions. HIGH-PRESSURES MACHINE In this machine (diagramed in Fig. 1) the mud, pore and confining pressures can all be adjusted independently. The foil-covered rock sample contained in the inner pressure vessel is confined by oil that is pressurized by means of a hand pump. The pore space of the watersaturated sample is connected to an arrangement which keeps the pressure in the pore space constant regardless of the rate of filtrate flow through the sample.

By J. L. Walter

Extra-low carbon iron sheet, when deformed and annealed, undergoes exaggerated or abnormal grain growth in the critically deformed regions of the sheet. This exaggerated pmth occurs, for low strains (3 to 6 pct), only in sheet which has a fine dispersion of precipitates in the subsurface region of the sheet and fewer and coarser precipitates in the sheet interior. These particles have been identified as manganese sulfides. Wing the anneal, grains near the surface are gvowth-inhibited by the fine particles but the grains in the interior are free to grow normally. With the additional driving force provided by the strain energy, the interior grains first grow into the small subsurface pains. Eventually, these growing grains grow completely through the sheet. Calculations of limiting grain sizes at various values of strain indicate that a volume fraction of precipitates in excess of 10-&apos; would be required to eliminate exaggerated growth in material strained to 10 pct. OPEN-COIL annealing has made decarburization of sheet steel both efficient and economically practical. Use of such material for porcelain-enameling stock is one of many possible applications of low-carbon iron since carbon in steel is deleterious to porcelain-enameling properties.&apos; However, the extra-low carbon iron presently available presents another problem, that of exaggerated grain growth in regions where the sheet has been deformed as by bending or stretching. In exaggerated grain growth a few grains start to absorb their neighbors and these may become very much larger than the average grains of the sheet. Other names for exaggerated grain growth are coarsening, critical grain growth, secondary recrystallization, abnormal grain growth, or discontinuous grain growth. While this grain growth does not affect the enameling qualities of the low-carbon iron sheet, their presence results in a marked reduction of tensile-yield strength in the region of the sheet containing the large grains. The loss of tensile yield strength may render the material unsuitable for many applications . This report describes the results of a study undertaken to determine the cause of the exaggerated grab growth in extra-1ow carbon iron and, if possi- ble, to prescribe practical procedures for its prevention. GENERAL THEORY The driving force for exaggerated grain growth is the grain boundary free energy. This driving force is proportional to (l/rl + l/r2) where rl and r2 are the mutually perpendicular radii of curvature of the boundary between the growing grain and the grain being consumed. Thus, the greater the difference in size between the growing grain and the matrix grains, the higher the driving force for grain growth. If, however, the matrix grains are free to grow simultaneously, the driving force for exaggerated growth will be diminished. Stability toward growth of the matrix grains may be caused by a) a strong single orientation texture (texture inhibition),&apos; b) a dispersed second phase,3"5 c) the thickness effect,&apos; or d) intergranular segregation.7"9 As exaggerated growth occurs when growth of the matrix grains has been slowed by the stabilizing processes mentioned above, there must be an additional factor acting to promote growth of a few of the grains to the point where they are enough larger than the matrix grains that boundary energy driving forces are sufficient to cause continued growth. For instance, at the annealing temperature, growth-inhibiting inclusions may slowly dissolve and coalesce. Eventually, a grain boundary becomes unlocked and migration occurs at the expense of neighboring grains. Or, an additional driving force may be supplied to some of the grains if the material is strained. Then, since some grains will be strained less than others, the difference in strain energy between adjacent grains may be sufficient to overcome boundary locking and allow growth of the grains with lower strain energies. In the present study, therefore, such factors as the presence or absence of dispersed phases, the nature of the exaggerated growth, and the effect of strain have been considered. EXPERIMENTAL PROCEDURE I) Material and Processing. Three types of low-carbon iron were used in this study; types A and B were commercial grades, each from a different supplier.* The precise details of the processing of

Jan 1, 1963

By W. P. Sykes

THIS investigation was undertaken primarily to establish the relations existing between temperature and mechanical properties in molybdenum, nickel, and an aluminum-copper alloy. Molybdenum (m.p. 2500° C.) was chosen because it is partly similar to tungsten and partly similar to the common ductile metals. Also it is known to furnish, by proper treatment, a desirable material to use in studying relation of grain size and physical properties. The molybdenum used was of the quality that is drawn into wire 0.003 in. in diameter for use as filament supports in incandescent lamps; chemical analysis shows less than 0.1 per cent. of impurities. Nickel belongs to the same class as iron. Its melting point is 1450° C. and an allotropic change at about 370° C. results in a loss of magnetism above that temperature. This feature made nickel doubly valuable for the purposes of these tests. The nickel used was obtained from the Driver-Harris Co. as 0.090 in. (2.3-mm.) wire, annealed; analysis showed 99.8 per cent. nickel and 0.150 per cent. iron. Aluminum is one of the low melting-point metals. Some tensile tests at elevated temperatures have been reported by Bengough but the possibility of learning more with the low temperature and sensitive apparatus available recommended this metal. The samples marked Al are an aluminum-copper alloy; they contained 3 per cent. copper, 0.42 per cent. iron, and 0.21 per cent. silicon. The presence of the copper somewhat complicates the analysis of the results; but the action of copper in aluminum has been studied so that its influence might have been foretold, in part at least. The material and analyses were furnished by the Aluminum Castings Co. The nickel wire, which was deformed at 400° C., was drawn under a bath of molten lead and through a die, which also was immersed in the bath. A thermocouple was suspended in the molten metal to indicate

Jan 1, 1921

By W. F. Campbell

One of the deepest coal operations today is the Springhill No. 2 mine of Cumberland Railway & Coal Co., subsidiary of Dominion Coal Co. Ltd. Mining is now conducted at a slope distance of 14,000 ft, with 4400 vertical ft of cover. The record of Springhill No. 2 can be said to contain the history of bumps in the Province of Nova Scotia. The Springhill coal field forms part of the Cumberland field of Carboniferous age. There are seven mineable fields in the area, numbered in the order they were discovered. Mining has been carried on in all but the No. 4 and 5 seams, but present operations are confined to the No. 2. Fig. 1 shows a vertical section through the seams. Opened in 1873, No. 2 mine was first worked from parallel slopes driven from the outcrop of No. 2 seam down to the 7700 level. As the mine went deeper, a two-place auxiliary slope was driven from the 6900 level to the present workings. A transfer level at the 7800 connects the main haulage with the auxiliary haulage slope. The No. 2 mine plan is shown in Figs. 2 and 3. The seam is bituminous, averaging 8.5 to 9 ft thick. There is a well defined parting 14 to 16 in. from the roof, and this roof coal is harder than the rest of the seam. Average pitch at the outcrop is 30°; at the 6500 level, 20°; at the 7900 level, 16°; and at the 13,800 level, 10°. Immediate roof and floor strata consist of beds of variable thicknesses of shales, grading to arenaceous shales to shaly sandstones to sandstones. A characteristic of the strata is the appearance and disappearance of sandstone bands, of considerable thickness, over distances of several hundred feet. MINE HISTORY Entrance to No. 2 mine is obtained by three parallel slopes, separated by 100-ft pillars except in the upper portion of the mine where the pillars are smaller. Main haulage levels were originally driven 600 ft apart for room and pillar extraction. A parallel drainage and intake airway was driven below each haulage level and a parallel return airway (counter level) above. Pillars 80 to 100 ft wide separated these two servicing entries from the center haulage level. Inclines up to 700 ft apart were driven off the levels up pitch to the upper levels, and at 40-ft centers level rooms 12 ft wide were driven off each side of the inclines, separated by crosscuts every 50 to 100 ft. The rooms were driven up to 350 ft or until they were holed into the room from the adjoining incline—a plan followed until the level reached its boundary. When the entire area between two levels had been divided into pillars, the pillars were extracted from the boundary back to the slope pillars. As depth of cover increased, mining conditions required larger pillars, and at the 3300 level, where NECESSARY PRECAUTIONS FOR MINING AT DEPTH In Room and Pillar Extraction: 1) Pillars must not be too small. 2) Pillar size must be uniform. 3) Extraction lines must be kept as straight and as uniform as possible. If they are irregular they should be brought back into line slowly. 4) Peninsulas of coal surrounded by gob must be avoided. 5) Pillars should not be disturbed after they have been formed. If it is necessary to increase the width of an opening, stripping or ribbing should be done gradually over a long distance. If increased width of openings is necessary at certain locations and can be anticipated, the openings should be widened during development. 6) Under no conditions should small pillars be left in the gob that would interfere with caving. In Long wall Operations: 1) Pillars formed during development for retreating longwalls should be uniform in size and shape. 2) Pillars should not be split after development, but if pillar splitting does become necessary it should not be carried out within the zone influenced by the working faces. 3) Width of levels should not be increased after the levels have been developed. If it does become necessary to widen a level it must be done gradually over a long distance by stripping or ribbing the coal ribs. 4) Extraction lines should remain uniform. If several walls are worked together—one behind the other—a uniform distance must be maintained between them and the wall faces must be kept as straight as possible. If the walls do get out of line, they must be brought back into line gradually to allow for a gradual change in the stress distribution over the area. 5) Stumps of coal, roof supports, etc. must not be allowed to remain in the gob to interfere with caving. 6) Midwalls should be built as rigidly as possible and properly maintained.

Jan 1, 1959

By E. S. Tankins, G. R. Belton

A simple solution model, based upon the formation of molecular species, is developed for strongly electronegative dilute solutes in liquid binary-metallic solvents. Two approximations are considered for the relative concentrations of the species: the random and the quasi-chemical. Equations are presented for the partial molar free energy, enthalpy, and entropy of mixing of the solute. An experimental study has been made of equilibrium in the reaction H2 6) +0 (dissolved) = H2O(g))for the liquid Cu-Co alloys. The standard free energy of solution of oxygen is presented as a function of composition for the alloys at 1550°C and as a function of temperature for five of the alloys. The experimental results for these alloys and also for Cu-Ni alloys are shown to be in reasonable agreernent with the theory in the random approximation. A knowledge of the thermodynamic behavior of dilute solutes in liquid metals and alloys is of importance in understanding and designing refining and alloy-making processes. Accordingly, several attempts have been made to derive suitable solution models to forecast the effect of a third component on the activity coefficient of such a solute in a metal. Alcock and Richardson&apos; reviewed the literature prior to 1958 and also showed that a regular solution model gave a reasonable description in the case of metallic solutes but failed to account for the behavior of the more electronegative solutes sulfur and oxygen. These same authors2 later modified their model by using the quasi-chemical approximation3 to calculate the average composition of the first coordination shell surrounding each solute atom. This modified model was shown to lead to a better qualitative description of the behavior of the electronegative solutes; however, quantitative agreement with experimental data for oxygen in alloys could only be achieved by assuming a very small coordination number. The authors concluded that the major source of error in the model was the assumption that pairwise interaction energies were independent of composition. Substitutional and interstitial random solution models by Wada and saito4 are essentially similar to the first model except that the required interchange energies were derived from the modified solubility parameter equation of Mott, instead of from experimental binary data. Most recently Hoch5 has presented a statistical model for interstitial solutions and has applied the model to the Fe-C-O system. However, as the various interaction energies needed in the model had to be derived from the ternary data, the model does not promise well as a means of forecasting ternary behavior. Each of the above models carries the assumption that the strongly electronegative solutes have the same configurational environment as metallic solutes; i.e., the solute can be treated as a substitutional or interstitial atom in a quasi-crystalline lattice and is surrounded by a normal coordination shell of solvent atoms. There are, however, a number of facts which suggest that this is unlikely. First, the heats of solution are large, being more typical of molecule formation rather than alloying. For example, the heats of solution of monatomic oxygen and sulfur in liquid iron are -90 kea16,8 and -74 kea1,7, 8 respectively. These are to be compared with maximum heats of solution of metallic solutes in liquid iron of about -13 keal (silicon is an exception with -28.5 kea17). The large depression of the surface tension of liquid iron by trace amounts of the electronegative solutes oxygen, sulfur, and selenium9 suggests, by analogy with aqueous systems, the possible existence of polar molecules in the liquid. The effect of these solutes is at least three orders of magnitude greater than normal metal solutes.10 As has been pointed out by Richardson,11 the electron affinities and ionization potentials of oxygen and sulfur are such that it is likely that they exist in metallic solution as negatively charged ions. If this is so, and it is assumed that electrostatic forces play an important role in determining the configuration, it is unlikely that the stable configuration will be that of an isolated ion surrounded by a symmetrical coordination shell of solvent ions. It is more likely that the energy of the system would be lowered by the formation of solute-solvent screened dipoles. The above arguments suggest the formation of "molecular species" between solute and solvent atoms. The idea of the existence of molecular species in such solutions is not new, however&apos;, for Marshall and chipman12 have explained in a semi-quantitative manner the C-O equilibrium in liquid iron by postulating the species CO. Chen and Chip-man13 interpreted their measurements on the Cr-O equilibrium in iron in terms of the species CrO. Zapffe and sims14 have also postulated the existence of such species in liquid-iron alloys.

Jan 1, 1965

By E. Miller, J. M. Eldridge, K. L. Komarek

Aclivilies of magnesium in liquid Alg-Si alloys have been delermined between 5 and 60 at. pcl Si, close to the melling point of Mg2Si, by an improved isopieslic melhod. Silicon specinrens, held in alumina crucibles and graplrile conlainevs of special design, were healed in a letrlpevalure gvadient and equilibrated with mag-nesilcrrl rapor in a closed lilanium system. The ther-madynamic Junctions were calculated and compared with the thermodyuamic properties of the other three mg- Gvoup IVB systems. Lattice paramelers of three Mg2X compounds were measured. The bonding in the Mg2X compounds is largely covalent with small and uarying amounts of metallic and ionic conlvibutions. The Mg-Si phase diagram1 has one congruent melting compound, Mg2Si, of essentially stoichiometric composition, two eutectics, and very limited terminal solid solubilities. Little information is available on the thermodynamic properties of this system. The free energy of formation of Mg2Si has been determined by the Knudsen cell technique2 in the range 572" to 680oC, by the transportation method3 between 858" and 950oC, and by the electromotive-force method4 in the range 400o to 600°C. Kubaschewski and villa5 and caulfield6 have measured the heat of formation of Mg2Si. An electromotive-force study of magnesium-rich liquid alloys was recently published by Sryvalin el al.7 The present investigation was undertaken to complete a general survey of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,a9,Mg-Sn,10,11 mg-Ge,12and Mg-Si. An isopiestic technique, previously developed for similar measurements on liquid Mg-sn11 and Mg-Ge alloys,12 was modified for the Mg-Si system. Specimens of the nonvolatile component, silicon, were contained in dense alumina crucibles placed inside covered graphite crucibles which were heated in a temperature gradient in an evacuated and sealed titanium reaction tube and equilibrated with magnesium vapor of known vapor pressure. The alumina crucibles prevented contact between the highly corrosive liquid Mg-Si alloys and graphite. The graphite cruci- bles effectively preserved the high-temperature equilibrium composition of the liquid alloys containing highly volatile magnesium on termination of the experiments during the quench to room temperature. EXPERIMENTAL PROCEDURE Silicon of semiconductor-grade purity (E. I. du Pont de Nemours and Co., Brevard, N.C.) and 99.99+ pct Mg (Dominion Magnesium Ltd., Toronto, Canada) were used. Graphite crucibles with press-fitted lids were machined from high-density (1.92 g per cu cm) rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The alumina crucibles had a purity of 99.7+ pct (Triangle RR grade, Morganite, Inc., Long Island City, N.Y.). In preliminary runs the liquid alloys were contained in graphite crucibles following the exact procedure developed for the Mg-Ge system.&apos;2 These runs failed due to appreciable reaction between the molten Mg-Si alloys and graphite, and the results have been discarded. The procedure was then modified and the Mg-Si alloys were subsequently held in alumina crucibles. For most of the runs alumina crucibles of known weight and approximately 6.3 mm ID, 12.5 mm height, 1.0 mm wall thickness were loaded with weighed amounts of silicon and encapsuled in tightly covered weighed graphite crucibles 5/16 in. ID, 2 in. helght, 3/32 in. wall thickness). The graphite crucibles were machined from rods which were 85 pct of the theoretical density. These crucibles were therefore sufficiently porous so as to permit magnesium vapor to effuse through the silicon under the experimental conditions of approximately 970O to 1220°C and 1 day equilibration time. However, negligible magnesium was lost from the crucible during the quench due to the slow effusion rate through the pores of the graphite. The inner alumina crucible prevented the liquid alloys from contacting the graphite, and the very tightly fitting graphite crucible lids served to retain any magnesium vaporizing from the alloys inside the crucibles during the quenching step.12 The loaded silicon-alumina-graphite cells were positioned, one above another, on a 16-in.-long titanium thermocouple well and tied securely to the titanium tube with thin molybdenum wires held in grooves around the circumference of the graphite crucibles. A thin (0.005-in.) molybdenum strip prevented contact between the graphite crucibles and the titanium. This assembly was lowered into a titanium reaction tube (la in. ID, 16 in. long, $ in. wall thickness) closed on one end which contained a 11/2-in.-long cylinder of magnesium at the bottom. The inner titanium thermocouple well was positioned eccentrically in the large tube because of the eccentric mounting of the cells on the well. Appropriate modifications of the titanium cap"&apos;12 were made to join the inner and outer titanium

Jan 1, 1968

By E. H. Bunce, H. M. Haslam

The "direct process" for the manufacture of pigment zinc oxide produces the oxide directly from ore. This is accomplished by reducing the zinc by means of carbonaceous fuels and immediately burning the evolved zinc vapor to zinc oxide. For many years this was done by smelting a loose charge of ore and fuel on perforated grates. Since this process was developed in America and was extensively used here, it has become known as the "American process." Alternative methods of producing pigment zinc oxide are the "indirect process " and the "wet process." In the indirect process the raw material is metallic zinc, which is volatilized and burned to the oxide. For a long time this has been done in externally fired horizontal refractory retorts. This process has become known as the "French process," from the country of its origin. The wet process precipitates the carbonate or hydrate from zinc-bearing liquors and then calcines the precipitate. This method has been but sparingly used for producing commercial quantities of zinc oxide. It appears to be advisable to restrict the use of the terms "American process" and "French process" to the methods of the earlier periods and to consider the terms "direct process" and "indirect process" as generic terms to designate, first, all methods of producing pigment zinc oxide directly from ores, and, second, to include all those methods of producing zinc oxide from metallic zinc and metallic zinc-bearing substances. American Process In 1796 John Atkinson was granted British Patent No. 2094/1796 entitled, "Manufacture of White Paint." This patent describes a method of producing zinc oxide in which roasted zinc blende or calcined calamine is mixed with charcoal, and the mixture heated in a muffle to liberate zinc vapor, which is then burned to obtain zinc oxide fume. About 1850 The New Jersey Zinc Co., at its plant in Newark, N. J., attempted to make zinc oxide by smelting, in a reverberatory furnace, a mixture of coal and ore from its Franklin mine. A considerable amount

Jan 1, 1937