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By H. W. Russell, Paul D. MILLER

IT is known that austenitic chromium-nickel steels that have free carbide in the grain boundaries are subject to intergranular corrosion. It is difficult to detect such a susceptible condition in a fabricated article because present test methods require a sample section for examination and in most cases this is difficult to obtain. The question of the nature and prevention of intergranular corrosion in austenitic stainless steels have been ably discussed by Bain and co-workers1-3 and by other investigators.4-10 The present methods of study subject samples to corrosive conditions in such reagents as the Strauss solution, a. mixture of copper sulphate and sulphuric acid. Such tests usually require at least 72 hr. to run. Various methods of measuring the degree of sensitization have been employed, such as the measurement of electrical resistivity, magnetic measurements, measurement of the degree of cracking produced on bending over a mandrel, and microscopic studies. The detection of carbides at the grain boundaries by metallographic polishing and etching methods is tedious and requires a skilled operator. A recent report on such methods of carbide detection is given by the American Society for Testing Materials Subcommittee VI of Committee A-10 11 and by Arness.12 The present investigation was undertaken to develop a simple test procedure for detecting carbide precipitation or susceptibility to intergranular corrosion. The test is designed for use in the plant and for the testing of fabricated structures. Carbide precipitation, the factor leading to susceptibility to corrosion, is produced by heating the alloy in the temperature range 800° to 1600°F., as in welding, in improper annealing or in service where such temperatures are met. The connection between such precipitation and susceptibility to corrosion has been thoroughly discussed, as has been the use of stabilizing addition elements to prevent precipitation. EXPERIMENTAL METHOD A small area of the steel under test is subjected to an anodic treatment in a cell that can be clamped onto a sample or an actual structure. The cell and electrical circuit used are illustrated in Fig. I. The cell C is lead, joined to the steel plate D and insulated from it by a short piece of rubber tubing E. The cell is forced tightly against the steel plate by a spring or clamping device. The seal formed by the rubber against the steel plate is sufficient to retain the liquid bath inside the cell. The spot treated can be made any shape desired, depending on the shape of the rubber gasket. The cell illustrated polishes a circular spot about 3/8-in. diameter. The bath consists of 60 per cent (by weight) sulphuric acid to which is added 5 ml. per liter of Glycyrrhiza extract (U.S.P.). The cell requires about 2 to 2.5

Jan 1, 1941

By R. S. Goodrich, G. S. Ansell

The microstructure of three Al-Al2O3 SAP-Type alloys (containing 2.0, 3.0, and 5.7 wt pct alumina, respectively) was studied utilizing transmission electron microscopy. These alloys were fabricated from aluminum powders by powder-metallurgical techniques, cold-rolled into thin strips, and recrys -tallized. Thin foils suitable for an electron-transmission study were then prepared from the strip material by electropolishing. The microstructure of these alloys is shown to consist of small (0.1 mean diameter) plate -shaped alumina particles finely distributed in an aluminum matrix. In the higher-oxide content alloys the platelets are somewhat larger and more irregular in shape. The distribution of oxide particles is not uniform and there is an increasing tendency toward clumping SINCE the discovery by Irmann1 that aluminum alloys produced by compacting, hot pressing, and extruding fine aluminum powders possess remarkable high-temperature mechanical properties, the Al-A12O3 SAP-Type alloys have been utilized extensively as model dispersion-strengthened alloys in both experimental and theoretical invest igations.2-8 The use of the SAP-Type alloys as model dispersion-strengthened alloys implicitly assumes that their microstructure has been completely delineated. This is, however, not the case. with increasing oxide content. In all the alloys studied, the mean center-to-center spacing of particles was quite small (0.2 u) due to the very fine oxide debris present. Selected-area diffraction of the specimen identified the oxide as either y Al2O3 or y' Al2o3. The re crystallized MD-5100 alloy exhibited a mean grain diameter of only 0.7u, while the grain size of the other alloys was several hundred microns. Severe pinning of the grain boundaries by oxide particles was rarely observed, and the grain boundary triple points in the small-grained MD-5100 alloy were often particle -free. Diffraction contrasts visible around the particles are attributed to elastic strain fields set up by differential thermal contraction during cooling from the recrystallization anneal. Early investigation demonstrated that optical metallography did not possess sufficient resolution to observe the microstructure of the SAP-Type alloys.' Later, extensive use was made of replication techniques to study the microstructure by means of electron microscopy.7-9 These studies indicated that the SAP-Type alloys consist of a dispertion of irregular Al2O3 platelets, approximately 150A thick 9 and a micron or so on edge,9 distributed in a matrix of commercial-purity aluminum. These oxide platelets tend to be oriented in the aluminum matrix, with their largest dimension parallel to the extrusion direction. 8,9 A study employing polarized-light techniques1' indicated that the grain size of a series of as-extruded SAP-Type alloys was several microns in diameter, while the grain size after re-crystallization was several millimeters in diameter. A more recent study 12 utilizing surface-replication techniques examined the particle morphology,

Jan 1, 1964

By J. Lindbo, B. Vigeholm

IN transmission electron microscopy, specimen thicknesses quoted are frequently based upon either traditionally familiar values or a few evaluations representing the whole material. Taking aluminum in 100 kv TEM as an example, average and maximum values are widely accepted as being 2000 to 2500 and 6000 to 7OOOÅ, respectively. It is the purpose of this note to revise these figures and to point out the importance of evaluating individual specimens carefully. All evaluations have been based upon slip trace widths and lattice orientations as determined from diffraction patterns. In many cases where two or more slip systems have been operating the geometrical method described by Crocker and Bevis1 has been applied as a check. The foils were usually oriented to within 2 deg from the exact Bragg angle. Kikuchi patterns were used as indications of correct orientations but not applied in the evaluations. The tilt of the foil surface relative to the beam normal may with certain geometrical relations between the tilt axis and the operating slip plane lead to substantial errors.2'3 Where these geometries were inevitable the samples were omitted in the investigations. Various measures were taken in order to overcome ambiguities, e.g., comparison with neighboring grains, tilts, evaluations based upon two or three slip systems,' and comparison with extinction contour evaluations where s = 0 conditions were obtained. Errors caused by misinterpretation of the slip traces on a micrograph are easily avoided by considering the bright-dark sequence on opposite surfaces and by taking into account the tapering of the foil usually leading to a distinguishable divergence of the pair of traces. In the investigations described here the interpretation was further facilitated as the slip trace formation was observed on the microscope screen and sketches taken down. In a few observations slipping was so violent that the distinction of pairs was considered dubious and consequently given up. To assess average values, thickness evaluations carried out in two independent investigations were analyzed: I) 99.998 pct A1 extruded, cold-drawn, and recrys-tallized to grain sizes between 35 and 500 um were deformed in tension at room temperature. In order to determine the dislocation densities as a function of strain,4 specimens prepared by spark machining and electropolishing in a PTFE holder were analyzed in the electron microscope at 100 kv. Thicknesses were evaluated for 569 selected areas. Histogram I in Fig. 1 shows the results, the average thickness being 4900Å. II) Electropolished specimens prepared from 99.9999 pct A1 with magnesium contents from 0.005 to 0.5 pct rolled to foil and annealed were subjected to fission fragment irradiationa2 For volumetric dose and defect concentration determinations thickness evaluations were performed on 123 areas. Histogram II in Fig. 1 shows the thicknesses of these areas averaging 4250Å. Whereas in investigation I no selection related to thickness has been made, some thin as well as thick areas have been omitted from I1 for experimental reasons. This and the application of two different microscopes although of the same type may account for the difference in average thickness. Assuming a mean error of 10 pct for a single evaluation, the error of the average should be negligible. In order to investigate the maximum transmissible foil thickness in aluminum, specimens were prepared from single crystals with (111) and (110) orientations parallel to the beam, and from polycrystalline material. Maximum values of thickness that could be measured were given by the stopping of the dislocations. The visibility often extended far beyond the end of the slip trace, but with no means of knowing the

Jan 1, 1970

By H. Kosmider, P. Coheur

New processes of blowing with an oxygen-enriched air or gas mixtures of oxygen and steam allow the steelmaker to produce, in a basic converter, a rimmed steel low in nitrogen (0.0020 pct), phosphorous (0.020 pct), and sulphur (0.020 pct). The physical properties (ductility) of the new steels are excellent. Furthermore, from the point of view of economy, these new methods of blowing offer outstanding possibilities. THE natural occurrence of geological deposits of iron ore and local economic circumstances led European blast furnace men to work large quantities of lean iron ore with a phosphorus content as high as 0.5 pct. The iron obtained from these ores generally contains 1.5 to 2.1 pct phosphorus, 3.6 to 3.9 pct carbon, 0.3 to 0.6 pct silicon, 0.04 to 0.08 pct sulphur, and 0.3 to 1.2 pct manganese. To produce steel from this pig iron, the steelmaker has at his disposal several processes. One of the simplest and most economical is the pneumatic process developed by S. G. Thomas in 1879. This process of steelmaking, called the Thomas process, consists of blowing through the bottom of a basic bessemer converter and is used widely in Western Europe, as shown in Table I. Due to the development of tonnage oxygen plants, this process has become more important because the use of oxygen offers new possibilities of steel manufacture. Not only may the quality of the steel be improved, but liquid pig iron also may be used, the composition of which does not meet the heat requirements of the blow with atmospheric air. It is not intended to present here a detailed scientific discussion of the basic bessemer process but rather to discuss briefly its industrial possibilities in the case of rimmed steel and when blowing with atmospheric air, oxygen-enriched air, or gas mixtures of oxygen and steam. This paper is based on the current practice at Klockner-Hüttenwerk Haspe's steel division, and at six Belgian and Luxemburg steel works. The latter are members of the Liege section of the C.N.R.M. (National Institute for Metallurgical Research) and are: ARBED, John Cocker-ill, Esperance-Longdoz, HADIR, Miniere et Metal-lurgique de Rodange, and Ougree-Marihaye, most of which are working with tonnage oxygen plants.' In order to avoid any misunderstanding, it should be noted that most of the techniques to be men- tioned, or similar ones, are used currently at many steel plants in Western Europe. Background The basic converters used in Europe have a capacity of 17 to 65 tons of steel, and are similar in shape to the one in Fig. 1. The lining is brick or rammed dolomite and has a life of 250 to 500 blows. The bottom is rammed dolomite and has a life of 40 to 80 blows. As far as we know, the type of blast used does not appear to have any influence on the life of the lining. Bottom life, on the contrary, depends very much upon the composition of the blast. It is only when

Jan 1, 1955

By E. A. Gulbransen, W. S. Wysong, K. Andrew

The reaction of carbon in solid solution in a metal with the surface oxide fim on many metals may be inferred from thermo-dynamic calculations for high vacua and high temperature conditions. Holm has recently shown that oxide films may be removed from ferrous materials by heating in a vacuum at high temperatures and that carbon is the essential element in the reaction. considerable work has been described in the literature on the de-carburization reaction. Several general references may been 2,3,4 However, the nature of the mechanism involved in the decarburization is not well understood. Our interest in this reaction resulted from many attempts to degas and to reduce by pure and dry hydrogen the surface oxides on strips of various types Of chrome-nickel alloys. Some of the early experiments On the behavior Of '3 pct chrome-iron in vacua of the order of 5 X lo' mm and at a temperature Of 600°C have been reported.5 These experi-merits showed a 'low reaction with the residual Oxygen Or water vapor in the system and no reaction with hydrogen. This is in accord with thermodynamic data which would lead to the prediction that it is extremely difficult to maintain a hydrogen atmosphere at 600' C pure enough to reduce Crz03 formed On the surface. The crystal structure of the superficial oxide film formed on 13 pct chrome- iron and Nichrome V has been investigated in the thin film range by Gulbransenr Phelps and Hickman,' and shown to be "203. It Was surprising to us to note that when a specimen of Nichrome V containing approximately 80 pet nicke1 and 20 pet chromium was heated to 850°C in a high vacuum, the specimen lost weight. The rate Of weight loss was very temperature sensitive. A study of this reaction in vacua and in a hydrogen atmosphere is the subject of this communication. Type Reactions Let us consider the various reactions which may occur when a metal is heated in vacua, in a hydrogen atmosphere, or in an oxygen atmosphere. The number and kind of reactions will depend upon the chemical nature of the metal, its alloying constituents and the location of the alloying constituents. The metals used in this study are chrome-nickel alloys of the heater type, They consist essentially of chromium, nickel and iron, small amounts of carbon, silicon and manganese and traces of zirconium, calcium, aluminum and magnesium. The trace elements are added to improve the lifetime and other characteristics of the alloy when used as a heater. Seven of the more important reactions with which we are going to be concerned here are as follows: 1. Metal . (gas) F? metal + gas — degassing of the metal 2. zM(s) + y }i Oi(g) M MIOu(s) -oxidation

Jan 1, 1949

By John E. Conley

The slate industry of the United States has shown a marked decline in value of products made annually since the peak year 1925, although there has been moderate improvement over the lean years 1932 to 1934. In 1940, the value of all slate products sold was approximately 5¾ million dollars for a total output of 473,450 short tons. The quantity sold was a little less and the value a great deal lower than the annual averages for the past two decades. Enormous quantities of waste materials result from the quarrying, splitting and milling of slate. Obviously, utilization of such waste material is desirable, not only from the viewpoint of economical operation but also for the purpose of conserving natural resources. One possible use is to produce expanded or puffed lightweight aggregate for use in concretes. Such concretes are strong enough for specific uses, and the advantage of lightness could be obtained in such structures as the walls and roofs of buildings, suspension-bridge roadways and various other applications where weight is a factor. Conceivably, these uses could consume an appreciable annual tonnage. Use of Waste Slates for Making Aggregates The lightweight-aggregate industry has been discussed elsewhere4,5 and need not be covered in detail in this paper. The materials commonly utilized are naturally occurring aggregates such as volcanic cinder, tuff and pumice; by-product materials, such as ordinary cinders and air-cooled slags; and the specially manufactured products, including Haydite, Pottsco, Gravelite, Cel-seal, Superock and Waylite. Slates, however, have not been given the consideration they merit, especially in the United States. In the British Isles, some work has been done3 on certain Welsh slates by the Building Research Station to stimulate the use of these wastes. Requirements for Raw Materials As pointed out by Hughes,4 the lightweight-aggregate industry is segregated in regions adjacent to large cities in order to localize the market and avoid the necessity of long freight haulage. Waste slate from the deposits of eastern Pennsylvania, northern Maryland, and Virginia would meet the basic requirement of ally low-priced structural raw material. One apparent advantage is attained when slate waste, normally discarded, is utilized in the manufacture of a by-product. Mining or quarrying costs usually have been assessed against the main product. Some additional grinding might be desirable, but this operation would be relatively cheap, as most slates grind easily. It is believed that virtually all slates, when properly heated, will expand to some degree. However, types that will expand from 3 to 7 times their original volume are preferred. Fig, I illustratcs the expansion of a Pennsylvania slate. The cube originally

Jan 1, 1942

By John E. Conley

The slate industry of the United States has shown a marked decline in value of products made annually since the peak year 1925, although there has been moderate improvement over the lean years 1932 to 1934. In 1940, the value of all slate products sold was approximately 5¾ million dollars for a total output of 473,450 short tons. The quantity sold was a little less and the value a great deal lower than the annual averages for the past two decades. Enormous quantities of waste materials result from the quarrying, splitting and milling of slate. Obviously, utilization of such waste material is desirable, not only from the viewpoint of economical operation but also for the purpose of conserving natural resources. One possible use is to produce expanded or puffed lightweight aggregate for use in concretes. Such concretes are strong enough for specific uses, and the advantage of lightness could be obtained in such structures as the walls and roofs of buildings, suspension-bridge roadways and various other applications where weight is a factor. Conceivably, these uses could consume an appreciable annual tonnage. Use of Waste Slates for Making Aggregates The lightweight-aggregate industry has been discussed elsewhere4,5 and need not be covered in detail in this paper. The materials commonly utilized are naturally occurring aggregates such as volcanic cinder, tuff and pumice; by-product materials, such as ordinary cinders and air-cooled slags; and the specially manufactured products, including Haydite, Pottsco, Gravelite, Cel-seal, Superock and Waylite. Slates, however, have not been given the consideration they merit, especially in the United States. In the British Isles, some work has been done3 on certain Welsh slates by the Building Research Station to stimulate the use of these wastes. Requirements for Raw Materials As pointed out by Hughes,4 the lightweight-aggregate industry is segregated in regions adjacent to large cities in order to localize the market and avoid the necessity of long freight haulage. Waste slate from the deposits of eastern Pennsylvania, northern Maryland, and Virginia would meet the basic requirement of ally low-priced structural raw material. One apparent advantage is attained when slate waste, normally discarded, is utilized in the manufacture of a by-product. Mining or quarrying costs usually have been assessed against the main product. Some additional grinding might be desirable, but this operation would be relatively cheap, as most slates grind easily. It is believed that virtually all slates, when properly heated, will expand to some degree. However, types that will expand from 3 to 7 times their original volume are preferred. Fig, I illustratcs the expansion of a Pennsylvania slate. The cube originally

Jan 1, 1942

By C. G. Durdaller, W. H. Robinson, G. M. Pound

The nucleation rate of the a (pay) to 0 (white) tin transformation was measured as a function of temperature and a tin particle size using an X-ray diffraction technique. The powder specimens of a tin were essentially monodisperse and the small dinzension of the particles of these specimens was varied from 13 to 75 p. Several types of nucleation sites of differing potency were fbund to be operative in the nucleation process, but it could not be determined whether these sites were on the free surface of the tin particles or within the volume. Assuming that they were on the free surface, the average density of the most potent sites was calculated to be 2.5 to 5.3 x 10' sites per sq cnz through the application of a Poisson distribztion finction to the isothermal data. Analysis of the temperature dependence' of the rate constmts at a given fraction transformed suggests that the active sites are regions of higher free energy and not catalytic interfaces. Appreciable induction periods were observed at the lower temperatures of transformation. Experimental studies1 of solid-solid phase transformations have led to the belief that the new phase nucleates at structural imperfections. The purpose of the present work was to learn more about the mechanism of nucleation in solids and the nature of the singularities at which nucleation occurs. In this investigation nucleation rates in the isothermal transformation of gray to white tin were measured by an X-ray diffraction technique using essentially monodisperse powders of gray tin. This particular phase transformation was chosen for study because it presented fewer experimental difficulties than most others. The experimental temperature-control problems were minimal because the two phases coexist in equilibrium at 13.3"C, and measurable transformation rates occur at temperatures only slightly above room temperature. The growth rate of the P phase into the a2 is sufficiently fast to make the measured transformation rate equivalent to the nucleation rate, provided that the particle size of the samples is small enough; for the experimental temperatures used in this study, the particle diameter must be less than 100 p. EXPERIMENTAL TECHNIQUE The P tin used in this study was obtained from Capper Pass and Son Ltd., North Ferriby, Yorkshire, England, and was of 99.999 pct purity. It was transformedS to the a phase and ground into a fine powder in an agate mortar. This powder was separated by a Roller air classifier into seven fractions whose dimensions, as determined by microscopic measurement of many thousands of particles, are given in Table I and whose distribution of size within each fraction is given in Figs. 1 and 2. The shape of the particles was roughly that of an oblate spheroid,

Jan 1, 1964

By W. C. Hagel, H. J. Beattie

Seven austenitic alloys of varions base compositions and minor-alloy additions were solution-treated, aged systematically between 1200oand 1800oF, and examined by X-ray and electron metallography. Intragranular preczpitations of µ, Laves, s, ?', Ni3Ti, and x phases were observed as a function of composition and aging time and temperatwre. Phase solubility limits were detevtnitzed within 100Fo intervals. These inter metallic compounds fall into two distinct general classes, and whichever class predomznates depends on base composition. It has become increasingly evident that multicom-ponent austenitic alloys are well characterized by their precipitation processes. Since certain groups of elements act as one, the relationships among these processes are reasonably simple; complete identification of such processes is usually attainable by a systematic aging study with a combination of techniques centered on microscopy and diffraction. Several nickel- and cobalt-base alloys illustrating cellular precipitation and its interaction with general precipitation were reported previously.1 The group of alloys covered in the present paper demonstrates precipitation-hardening reactions involving two distinct classes of intermetallic compounds where the predominating class appears to depend on base composition. This dependency ties in with a crystal-chemistry regularity first observed some twenty years ago by Laves and Wallbaum but never amplified to our knowledge. Results of electron-microscope and X-ray diffraction studies on systematically aged hot-rolled alloys known commercially as S-816, S-590, Rene-41, Incoloy-901, M-308, and M-647 are reported here. Some of these alloys have previously undergone minor-phase analyses by other investiators. Alloy S-816 was investigated by Rosenbaum, Lane and Grant,3 and Weeton and Signorelli.4 Rosenbaum found only CbC in hot-rolled bars. Lane and Grant found CbC and a small amount of M6C in the cast structure and stated that both carbides form during aging, most of the precipitation being CbC. Weeton and Signorelli found CbC, M23C6 and a weak indication of a phase after a slow step-down cooling cycle from 2250°F. Rosenbaum also investigated hot-rolled samples of S-590 and identified CbC and M6C. Preliminary information on Rene-41, gained partly from the present work, was reported by Morris.5 Long-time precipitation phenomena in Incoloy-901 at 1350°Fwere investigated by Clark and Iwanski.B heir raw data re- semble those of our present heat with 0.1 pct B, while their interpretation of these data resembles our interpretation of data from another heat with only 0.001 pct B; they made no statement as to boron content. No previous minor-phase studies of alloys M-308 or M-647 have been reported. EXPERIMENTAL METHODS Table I gives alloy compositions in both weight and atomic percent. Specimens were solution-treated from 1700º to 2200ºF, aged at logarithmic-time intervals up to 1000 hours between 1200 and 1800 F, and examined in accordance with procedures previously described in detail. ' ' Phase extractions were carried out in electrolytic cells containing 800 ml of either 7 pct HC1 in denatured ethanol or 20 pct H3PO4 in water. After electrolysis for 48 hr at 0.1 to 0.2 amp per sq inch, residues were separated by filtration or centrifuging. X-ray powder patterns of residues were recorded on a diffractometer for accuracy and on film for sensitivity. Lattice parameters were calculated by least-squares analyses of indexed sin 8 values, and relative abundances were estimated from intensities of strongest lines of each phase. These phase abundances denote relative amounts with respect to each other rather than to the alloy. Mechanically polished specimens were etched in a freshly mixed solution of 92 pct HC1, 5 pct H2SO4, and 3 pct HNO3. Parlodion replicas for the electron microscope were chromium-shadowed in high vacuum at a glancing angle of 20deg. All electron micrographs are reproduced here with the shadowing source above. The correspondence betweenelectronmicrostructures and phases identified by X-rays was established by a high redundancy of correlation between relative amounts at different stages of aging and examination above and below critical transformation or solubility temperatures. EXPERIMENTAL RESULTS S-816 and S-590—The phases found in S-816 and S-590 after various aging and solutioning treatments are listed in Table 11. These data and the observed

Jan 1, 1962

By B. H. Caudle, A. B. Dyes, R. A. Erickson

The study of the influence of fluid mobilities on the sweepout pattern resulting from the injection of gas or water has been extended to cover the production period which follows breakthrough of the injected material. Mobility ratios over the range common in field operations (0.1 to 17) were studied for several pattern floods (five-spot, staggered, and direct line drive). The experimental data required for these studies were obtained by the use of the x-ray shadowgraph technique using miscible oil phases of different viscosities in porous plate mode1s of a reservoir element. From the shadowgraph pictures obtained before and after breakthrough of the injected fluid, flowing ratios at the producing well and cumulative volumes injected were calculated. The method for applying such data in predicting field behavior is illustrated for a water flood of a five-spot. For this case a range of mobility ratios of 0.5 to 5.0 results in: (I) nearly complete (95 to 100 per cent) sweepout pattern efficiencies at abandonment conditions, (2) production after breakthrough being responsible for as much as one-third of the total recovery at the lower mobility ratios, and (3) a twofold variation in the operating life of the reservoir. In determining the merits of a secondary recovery operation, the fraction of the reservoir which is ultimately to be swept by the injected fluid is of major importance. Because of its significance a large amount of research has been applied to the study of areal sweepout efficiency. Muskat, Wyckoff and Botset1,2 have presented the classic analysis of the pattern efficiency at breakthrough for several injection patterns in which the mobility of the fluids ahead of the injected phase front was equal to the mobility of the fluids behind the front. Aronofsky3 as extended this analysis of recovery at breakthrough through numerical computations and by the stepwise use of the potentiometric model to include the effect of different fluid mobilities ahead of and behind the invasion front on the line drive performance. Fay and Prats' have also employed numerical computations to show the influence of one other condition of fluid mobilities on the five spot flood. In a previous paper' a new method of attack on this problem which employed x-ray and porous plates was described. At that time experimental results were also presented which described the effect of fluid mobilities on the reservoir area contacted by the injected fluid at breakthrough for the five spot and direct line drive patterns. Most of the literature pertaining to sweepout pattern efficiency has emphasized the pattern which is obtained at breakthrough of the injected phase. The increase in the sweepout pattern which occurs after breakthrough

Jan 1, 1955

By N. A. Ziegler

THE chief difficulty in determining oxygen in steels is its tendency to form a variety of compounds. Almost every element, found as an ingredient in steels, maybe expected to be present as an oxide. Some of these oxides have widely differing properties, and consequently behave differently when attempts are made to reduce them by the vacuum fusion method. As I pointed out in a paper published in the Transactions of the A.S.S.T., Vol. 20, No. 1, many experimenters are spending considerable time and effort in attempting to deter¬mine the degree of completeness of the above reactions, and hold different opinions on the matter. In studying this subject the following table, taken from Hodgman and Lange's "Handbook of Chemistry and Physics" may be used as a guide.

Jan 1, 1933

By Reed W. Hyde

SOME information has been published on the sulphur dioxide concentration of gases from Dwight-Lloyd machines sintering lead ores but most of this relates to the customary practice in which the charge is relatively high in lead and is sintered in two passes over the machine. It is thought, therefore, that the following observations on sintering in one pass a low-lead, low-sulphur charge may be of interest. The data were obtained in sintering lead sulphide flotation concentrates mixed with minus 20-mesh oxide ore, the mixture carrying 16.8 per cent Pb and 5.3 per cent S. No returns were used because of the limited amount of sulphur available as fuel, but the mixture pelletized readily to make a satisfactorily permeable bed on the sintering machine. As there was a possibility that the SO2 might be utilized, a series of runs was made to determine the concentration of S02 in the gases at different points along the wind box, and the effect on this concentration of changes in the wind-box vacuum. Several runs each were made with vacuums (as measured in inches of water at the wind box) of (1) 2 to 1 1/3 in., (2) 4 to 3 1/2 in. and (3) 6 to 5 1/8 in. The averages of the determinations from each series are platted on the graph (Fig. I). The vertical scale shows the percentage by volume of SO2 (as determined by the Reich method), and the horizontal scale shows the time expressed as percentage of the total sintering time. Sintering was considered to be complete when no S02 could be detected in the gases. In all cases the depth of bed was 4 ½ in. and the weight of dry charge per square foot of hearth area was 45.2 lb. Other data are given in the table. The volume of gases corresponding to the several points along the wind box at which S02 determinations were made could not be measured, but has been calculated from the S02 content and sulphur elimination on the assumption that the volume is uniform throughout the sintering period. This is not strictly true, as with a given vacuum the volume will usually drop slightly toward the middle of the period and increase toward the end. However, this assumption is a reasonable approximation. Several interesting features are brought out by these data. In general, the published data on S02 concentration in sintering under ordinary conditions show a high S02 concentration in the early stages followed by a rapid decrease in concentration and with relatively little SO2 in the gases from the last half or third of the operation. In other words, the greater part of the sulphur elimination is obtained in the first third or half of the period. In these runs, the 6-in. vacuum, which approximates the usual operating condition, gives a curve that follows this customary pattern. Maximum S02 concentration is obtained 2 ½ min. after

Jan 1, 1942

CONTENTS PAGE THOENEN, J. R.-Limestone Production as a Mining Problem. Discussed by Oliver Bowles, J. T. Singewald, S. R. Russell 1 GRIGGS, C. C.-Engineering in Limestone Production. Discussed by W. C. Phalen, John Rice, Samuel M. Shallcross, Oliver Bowles, Nathan C. Rockwood, George Milliron 2 WILDER, FRANK A.-Rotary Calciners for Gypsum. Discussed by L. K. Arm-strong 9 PORTER, JOHN J.-Manufacturing Problems of Cement Industry. Discussed by Samuel M. Shallcross 9 KIRKHAM, VIRGIL R. D.-Phosphate Deposits of Idaho and Their Relation to the World Supply. Discussed by F. A. Wilder, S. L. Willis, G. R. Mansfield, R. W. Stone, L. K. Armstrong 9 Limestone Production as a Mining Problem Discussion of the paper of J. R. THOENEN, presented at the New York Meeting, February, 1925, and issued, as Paper 1417-H, with MINING AND METALLURGY, February, 1925. OLIVER BOWLES, New Brunswick, N. J.-I am so thoroughly convinced of the growing importance of underground work in the production of limestone that I had the author make a detailed study of limestone mining for the Bureau of Mines and prepare a report on the principles of limestone mining. Many limestone operators, long accustomed to open¬pit work, are being forced to mining. About 6 months ago I thought there were twenty-five or thirty underground limestone operations in the United States but the author has been finding new ones until his list now runs nearer sixty. Some of these are very extensive; one at least has 4 ½ miles of underground workings. There is an ever-expanding field for the engineer in the operation of limestone mines and quarries. Some of the larger companies realize the need of skilled engineering advice, but many of the companies regard the engineer as an unnecessary expense. Although almost every metal mine, even those handling only a few hundred tons of ore per month, employs a mining engineer, many limestone operations ten times as large employ no mining engineers. Few mining engineers are at all familiar

Jan 6, 1925

T. W. ROBINSON, Pueblo, Colo.: Mr. Potter's review is a striking testimony to the important part played by science in this branch of practice. But, the question arises, In which department has science effected most ? The available raw material, the size of furnaces, the general design and equipment of the plant, and the daily management, are particulars, each of which contributes to the general result, while the effect of each merges into that of the others. The following notes concerning the operations of the furnace-plant of the Colorado Fuel and Iron Company (formerly the Colorado Coal and Iron Company), at Pueblo, may throw some light upon the question of their relative importance. This company operates three stacks, and when the plant first came under my observation, about nine months ago, the furnaces were constructed, equipped,and run as stated below: Raw Materials.—The main sources of ore-supply were, as they still are, the Orient and Calumet mines of the company. The Brecce and Morning Glory ores, mentioned below, were formerly brought from Leadville, but are practically now no longer used. The Orient ore is a porous brown hematite, easily reducible in the furnace. The Calumet is a magnetite, very refractory in character, requiring preliminary roasting. Both are fairly uniform in composition. The Breece and Morning Glory are red hematites, resembling in appearance the soft ores of the Vermilion range, Lake Superior. The coke here used is made of coal from the company's mines in southern Colorado, and is distinct from that produced by the company in the western part of the State. The structure is similar to that of Alabama coke. The limestone employed is a calcite. The analyses are given in Table I. I would note, parenthetically, that I know of no section of the country presenting harder conditions for furnace-practice than these materials impose. Results cannot be measured by the more

Jan 1, 1894

By J. F. Olk, E. D. Spaulding, R. E. Thurmond, G. A. Komadina, R. W. Hernlund, J. A. Journeay

THE Pima pit is a 1700x1400-St oval, the long T axis parallel to the strike of the orebody. The north side of the pit is carried as a final pit slope that coincides with the footwall of the orebody. The south side and east and west ends of the pit are working slopes continually being stripped back toward the final slopes. An inclined roadway extending from the natural ground surface on a 5 pct grade down to the north- east corner provides access to the pit. This road enters the pit 130 ft below the natural surface and continues as a pit ramp on a 5 pct grade to the 3150-ft bench (roughly the base of the alluvial cover). At this point the ramp system is steepened to a 12 pct grade and continues to the pit bottom. The 5 pct grade is maintained in the alluvial section to facilitate scraper haulage out of the pit. In addition to this main access ramp, temporary working ramps in the alluvial areas allow shorter routes to dumps. These are left on top of working benches and do not change the overall working slopes. Below the base of the alluvium, haulage is by truck down to the skip loading point or up from the bottom to the skip loading point.

Jan 4, 1958

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

Established as a Division November 17, 1948 T D Jones, Chairman O C Ralston, Past Chairman R R. McNaughton, Chairman-elect B. W Gonser '53, Vice-Chairman P. T. Stroup '54, Vice-Chairman Ernest Kirkendall, Secretary 29 West 39th Street, New York City

Jan 1, 1952

By J. Rourke, F. S. Minshall, E. G. Zukas, C. M. Fowler, O&apos

The Hugoniot curves were determined for Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si. The pressure of the transition increased as the silicon content of the alloy increased. Single crystals of 2.9 wt pct Si-Fe were also studied. The pressure of the transition was not dependent on crystallo-graphic orientation. All of the Neumann bands (mechanical twins) were attributable to (112) planes but not all of the {112} planes showed twin markings. A thorough study of the iron Hugoniot (the relationship between specific volume and pressure) under plane wave shock loading revealed a pressure transition at about 130 kbar shock pressure. The results of this investigation were reported by Bancroft, Peterson, and inshall1 in 1956. At the time of this discovery, it was felt that this was probably the a, to y transition normally found in iron and many of its alloys. Subsequently a number of iron alloy systems were surveyed in which the alloying element has a considerable effect on the normal a, to y transformation. The influence of carbon and nickel and/or chromium have already been reported.2,3 At the present time, there appears to be some doubt that this pressure transition is the usual a, to y transition In this study, Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si were chosen for several reasons. To the present, the transition has been found only in iron-base alloys which were originally in the a, phase (bcc). Secondly, the y loop at atmospheric pressure extends to only about 2.5 wt pct Si. If the transition were a, to y, then one might expect a rather drastic pressure effect for alloys containing more than 2.5 wt pct Si. Finally, single crystals of Fe-Si alloys large enough for shock loading studies are readily available thereby making it quite easy to determine the effect of crystal orientation on the transition pressure and on the twinning behavior of the alloy. EXPERIMENTAL PROCEDURE Fe-Si alloys containing up to 7 wt pct Si were produced by normal vacuum casting procedures. Single crystals of Fe-2.9 wt pct Si were purchased from Monocrystals Co., Cleveland, Ohio. The orientations of these crystals were determined and samples cut so that the shock wave would be parallel (to within 1.5 deg) to either the (loo), (Ill), or (112) principal orientations. Three distinct experimental testing techniques were used. First, the pin technique, described elsewhere,4 was used to determine the transition pressure for the polycrystalline alloys as well as for the (111) and (112) orientations of the 2.9 wt pct Si single crystals. Secondly, the recovery studies, described in detail in an earlier paper,2 were used for determining the effect of alloy composition and crystal orientation on the plastic II compression-plastic I rarefaction interaction zone for several specific shock pressures. Finally, measurements of pressures above the two-wave threshold were made on the polycrystalline alloys so that more complete Hugoniot curves could be constructed for this alloy system. The optical techniques described by Rice et al.5 were used to measure the shock and free surface velocities of the samples from which the Hugoniot data were obtained. This method is applicable only in the single wave region, since velocities are obtained from the measured total transit times of the disturbances through measured sample thicknesses.

Jan 1, 1963

By E. A. Anderson, P. W. Ramsey, E. J. Boyle

Only a few zinc-rich alloys are in commercial use today, and these depend largely upon solid solution effects for their desirable properties. Typical examples are rolled alloys containing about 1 Per cent of copper, with Or without additions of elements such as magnesium, and die-casting alloys containing about 4 Per cent of aluminum with small amounts of magnesium and sometimes copper." A number of elements are capable of forming alloys with zinc, Which do not enter into solid solution except in limited degree. The Present Paper considers One such system, zinc-titanium, in which alloys having potentially useful properties in the rolled form were found. Zinc-titanium System The zinc-rich portion of the zinc-titanium diagram, as determined by standard methods in this laboratory,3 is shown in Fig. I. The portion of the diagram of significance in the present work extends from 0 to about 0.5 per cent titanium. Gebhardt4 places the eutectic at 0.45 per cent, but the evidence in favor 01 the composition given in Fig. I is considerable. The solid solubility of titanium in zinc is very low indeed and possibly places these alloys in a somewhat different category from the commercial alloys previously mentioned. Alloy Preparation All of the alloys used in this work were prepared with titanium metal of 98.9 per cent purity. In most cases high-purity zinc (99.99 per cent) was used but sufficient work was done later to show that zinc of about high-grade composition would yield approximately equal results. Best practice in alloy manufacture seemed to be to prepare a zinc-titanium hardener by adding about 4 per cent of titanium metal to molten zinc and holding under a boric acid cover, with frequent stirrings, at 750°C, until the titanium had dissolved. The desired titanium content could readily be obtained in the final alloy by adding the calculated amount 01 this hardener. The alloys proved to be quite stable in composition, unless overheated, and, with reasonable temperature control, required no cover or flux to prevent loss of titanium content by oxidatioll, Hot-rollig Tests Three alloys containing, by analysis, 0.05, 0.12, and 0.23 per cent titanium were selected for preliminary study. Slab cross sections a a marked grain refinement* (Fig. 2) in the two alloys of highest titanium content. Cast unalloyed zinc has a columnar grain structure similar to that shown for the alloy of lowest titanium content but without the scatter of small equiaxed grains at the center.

Jan 1, 1944

By P. W. Ramsey, E. J. Boyle, E. A. Anderson

Only a few zinc-rich alloys are in commercial use today, and these depend largely upon solid solution effects for their desirable properties. Typical examples are rolled alloys containing about 1 Per cent of copper, with Or without additions of elements such as magnesium, and die-casting alloys containing about 4 Per cent of aluminum with small amounts of magnesium and sometimes copper." A number of elements are capable of forming alloys with zinc, Which do not enter into solid solution except in limited degree. The Present Paper considers One such system, zinc-titanium, in which alloys having potentially useful properties in the rolled form were found. Zinc-titanium System The zinc-rich portion of the zinc-titanium diagram, as determined by standard methods in this laboratory,3 is shown in Fig. I. The portion of the diagram of significance in the present work extends from 0 to about 0.5 per cent titanium. Gebhardt4 places the eutectic at 0.45 per cent, but the evidence in favor 01 the composition given in Fig. I is considerable. The solid solubility of titanium in zinc is very low indeed and possibly places these alloys in a somewhat different category from the commercial alloys previously mentioned. Alloy Preparation All of the alloys used in this work were prepared with titanium metal of 98.9 per cent purity. In most cases high-purity zinc (99.99 per cent) was used but sufficient work was done later to show that zinc of about high-grade composition would yield approximately equal results. Best practice in alloy manufacture seemed to be to prepare a zinc-titanium hardener by adding about 4 per cent of titanium metal to molten zinc and holding under a boric acid cover, with frequent stirrings, at 750°C, until the titanium had dissolved. The desired titanium content could readily be obtained in the final alloy by adding the calculated amount 01 this hardener. The alloys proved to be quite stable in composition, unless overheated, and, with reasonable temperature control, required no cover or flux to prevent loss of titanium content by oxidatioll, Hot-rollig Tests Three alloys containing, by analysis, 0.05, 0.12, and 0.23 per cent titanium were selected for preliminary study. Slab cross sections a a marked grain refinement* (Fig. 2) in the two alloys of highest titanium content. Cast unalloyed zinc has a columnar grain structure similar to that shown for the alloy of lowest titanium content but without the scatter of small equiaxed grains at the center.

Jan 1, 1944