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By F. W. Steadman, Charles S. Barrett

Deformation bands of surprising regularity are found in large-grained poly-crystalline copper after cold-rolling (Fig. I). Individual bands frequently are large enough to permit a determination of their orientation by means of etch pits and an optical goniometer. Measurements have been made on 21 areas in seven different grains, and these, combined with X-ray studies of nine single crystals that had been cold-rolled after mounting in a polycrystal-line block, have contributed to a better understanding of the preferred orientations in rolled copper just as similar studies have for rolled iron1 and brass.2,3 Particular attention was given to determining orientations that are stable during rolling and to the manner of fragmentation and rotation of unstable grains. The possible role of twinning was also carefully investigated. The texture of polycrystalline copper after cold-rolling is well established by the pole figures that have been plotted by Schmid and Staffelbach,4 Iweronowa and Schdanow,6 and Brick and Williamson,8 all of which are in substantial agreement. There has been some divergence in the list of individual "ideal" orientations that have been used to describe the texture by these observers and others," although the orientation (110) [II2]—that is, (110) parallel to the rolling plane and [TIP] parallel to the rolling direction—is generally recognized as the most prominent orientation and (112) [III] one of the lesser orientations. Other orientations have been given by some observers as (236) [535], (100) [00I], and (110) [00I]. The texture of copper has also been described as (I35) [533].6,7 The sum of these orientations provides a reasonable approximation to the complete pole figure, but it does not follow that these specific orientations are necessarily of fundamental significance, for the choice of indices is arbitrary, within limits. Furthermore, a detailed investigation of the ideal orientations in cold-rolled iron discloses continuous ranges of equally favored positions rather than definite positions of high stability,' and similarly Brick's observations in a single crystal of a brass2 suggest that all orientations in the range between (110) [II3] and (110) [II7] are about equally stable. Materials and Methods The material used was vacuum-cast electrolytic copper kindly supplied by L. L. Wyman, of the General Electric Co.* Slicec 1/2 in. thick and 21/2 in. square, cut from the ingot, were rolled with 50 per cent reduction per pass to final thicknesses between 0.02 and 0.04 in., and etched to develop cube-face etch pits suitable for goniometric work.8 The etch was light on some strips and deep in others.

Jan 1, 1942

By G. L. Corrigan, J. R. Coleman

Four factors that largely determine the end product obtained when cement and water are mixed are the chemical compo ition of the cement, the fineness to which the cement is ground, the amount of mixing water used, and the procedure used in mixing the slurry. In order to study the effect of two of these factors, the other two, the chemical composition and method of mixing, are kept constant, leaving as variables fineness and water-cement ratio. Through years of experimentation and usage it has been well established that the reduction of cement clinker to a very fine state by grinding improves its cementing value, principally because the reaction between cement and water takes place only at the surface of the cement particle, further action being hindered by the accumulation of reaction products that tend to coat the unreacted material. Therefore, the more finely ground a cement, and the greater the surface exposed in proportion to its mass, the more rapid is the hydration rate. Similarly, the greater the surface exposed, the greater the proportion of the cement that reacts, and the lower the amount of residue that is unreacted and so remains inert and unable to make any contribution to cementing properties.1 Although it is more expensive to manufacture a finely ground cement than a coarser cement, the advantages of fine grinding of construction cements were so marked that the fineness of cement has increased considerably in past years. When the manufacture of special oil-well cements was begun, it was necessary to consider properties of cement that previously were considered of minor importance, foremost of these being pumpability. Since, with the water-cement ratio constant, a finely ground cement will produce a neat slurry of higher consistency and shorter time of pumpability than will a coarser cement, there is a tendency to grind oil-well cements to a lower degree of fineness. Therefore, in order to produce oil-well cements that will make a slurry having a long time of pumpability, cements are manufactured that because of their coarseness generally are poorer cementing materials than some of the more finely ground construction cements. On the other hand, often it is necessary to pump oil-well cements for long periods of time to place them properly behind a string of casing in a deep well, and since high strength is not of foremost importance for such cement, there is room for considerable controversy concerning the proper fineness range.

Jan 1, 1941

By W. J. Reagan

In a study of the life of ingot molds, it is essential to eliminate all of the variables. In the commercial manufacture of steel this is almost an impossibility. In this study many of the variables have been eliminated, and because of the unusually consistent furnace practice, with small variations in the type of steel manufactured, and a similar type of mold design for all ingot sizes, it is possible to determine with some degree of accuracy the cause of variations in ingot-mold life. All of the ingot molds in this study were used in the production of basic open-hearth killed steel with chemical analyses within the following range: C, 0.50-0.85 per cent; Mn, 0.60-0.80; Si, 0.20-0.30; S, 0.04 max.; P, 0.04 max. All ingot molds were of the closed-bottom type and used for bottom casting only. None of the molds in the study failed from cutting of the sides due to top casting; in fact, on only rare occasions are any molds used for top casting. The general type of this mold is shown in Fig. 1. All sizes have rather a heavy band of metal, about 6 in. wide, at the top to give mechanical strength at this point, and all have cast lugs. Cross sections of the various sizes from top and bottom sections are shown in Fig. 2. Ratios of wall thickness to ingot weight, ratio of ingot diameter to ingot length, and other figures of interest are shown in Table 1. In the majority of cases, the cause of failure in this type of mold is due to heavy fire cracking on the "flats" at a point from 3 to 6 in. from the bottom radius of the mold. Fig. 3 pictures this type of failure. The start of failure at these points usually begins with a very small section of the interior surface becoming involved. As a rule, a section of 1 or 2 sq. in. is the first noticeable indication that mold failure is taking place. Gradually the small section increases until a sizable cavity develops, causing a protuberance on the bottom of the ingot, which eventually becomes too large to be stripped. The mold is then removed from service. At the time of failure, this cavity often reaches a size of about 5 sq. in. and about 1/2in. deep. Sometimes cavities are found on only two or three sides and at other times all twelve sides appear to be invoIved.

Jan 1, 1937

By Charles S. Barrett, F. W. Steadman

Deformation bands of surprising regularity are found in large-grained poly-crystalline copper after cold-rolling (Fig. I). Individual bands frequently are large enough to permit a determination of their orientation by means of etch pits and an optical goniometer. Measurements have been made on 21 areas in seven different grains, and these, combined with X-ray studies of nine single crystals that had been cold-rolled after mounting in a polycrystal-line block, have contributed to a better understanding of the preferred orientations in rolled copper just as similar studies have for rolled iron1 and brass.2,3 Particular attention was given to determining orientations that are stable during rolling and to the manner of fragmentation and rotation of unstable grains. The possible role of twinning was also carefully investigated. The texture of polycrystalline copper after cold-rolling is well established by the pole figures that have been plotted by Schmid and Staffelbach,4 Iweronowa and Schdanow,6 and Brick and Williamson,8 all of which are in substantial agreement. There has been some divergence in the list of individual "ideal" orientations that have been used to describe the texture by these observers and others," although the orientation (110) [II2]—that is, (110) parallel to the rolling plane and [TIP] parallel to the rolling direction—is generally recognized as the most prominent orientation and (112) [III] one of the lesser orientations. Other orientations have been given by some observers as (236) [535], (100) [00I], and (110) [00I]. The texture of copper has also been described as (I35) [533].6,7 The sum of these orientations provides a reasonable approximation to the complete pole figure, but it does not follow that these specific orientations are necessarily of fundamental significance, for the choice of indices is arbitrary, within limits. Furthermore, a detailed investigation of the ideal orientations in cold-rolled iron discloses continuous ranges of equally favored positions rather than definite positions of high stability,' and similarly Brick's observations in a single crystal of a brass2 suggest that all orientations in the range between (110) [II3] and (110) [II7] are about equally stable. Materials and Methods The material used was vacuum-cast electrolytic copper kindly supplied by L. L. Wyman, of the General Electric Co.* Slicec 1/2 in. thick and 21/2 in. square, cut from the ingot, were rolled with 50 per cent reduction per pass to final thicknesses between 0.02 and 0.04 in., and etched to develop cube-face etch pits suitable for goniometric work.8 The etch was light on some strips and deep in others.

Jan 1, 1942

By R. L. Huntington, Frank P. Vance, George F. Russell, Robert Thompson

With the advent of higher pressures in the operation of natural-gas transmission lines, the removal of water vapor from the gas has become increasingly important in order to prevent condensation or formation of gas hydrate from slowing down or stopping the flow of gas. Intelligent design of these dehydration or gas-drying plants has been hampered through the Iack of experimental data on the water vapor content of natural gas at elevated pressures. In view of this need, this present investigation was sponsored by the Southern Natural Gas Co. in the Chemical Engineering laboratories at the University of Oklahoma Research Institute. Experimental results were obtained on the water-vapor content of natural gas up to 2000 lb. per sq. in. at atmospheric temperatures. The water content at 2000 lb. is approximately two thirds as much as it is at 1000 Ib. Deviations from the ideal gas laws vary directly with pressure and indirectly with temperature. Introduction The removal of water vapor from natural gas is an important operation in connection with the production and transportation of this commodity because: I. Liquid water accelerates internal corrosion of a pipe line. 2. Accumulation of water at low points in a pipe line reduces markedly its capacity. 3. Gas hydrates, icy snowlike growths, form readily under high pressure in the presence of the lower hydrocarbons and water, often plugging up the pipe line. In order to design dehydration plants for stripping the gas of its water content, it is essential that the engineer. have a knowledge of the saturated or equilibrium water-vapor content of the gas to be processed. With the gradual increase of operating pressures around gas-producing wells and pipe lines, it was observed that the quantity of water recovered from dehydration plants or condensed in colder lines was considerably greater than had been expected from calculated contents, based on vapor-pressure data taken from steam tables. This observation prompted a number of investigators, for instance, Laulhere,3 Dea-ton,l and Hammerschmidt2 to carry out experimental work at pressures up to 600 lb. per sq. in. in order to determine quantitatively the water content of various gases. Sage, Lacey, et al.4,5 have recognized more recently the need for such data at higher pressures, but their work was done at temperatures of 100ºF, and higher. Since hydrate formation usually, if not entirely, occurs at temperatures below 100ºF., the present investigation was confined to the . lower temperature range at pressures from 600 to 2000 lb. per sq. in. gauge.

Jan 1, 1945

By F. J. Meringer, C. W. MacGregor

Various investigations have been carried out to determine the effects of cold-rolling on the common physical properties as represented by the yield strength, tensile strength, percentage of elongation and ordinary reduction of area. Very little information is available in the literature with reference to the effects of cold-rolling on the true stress-strain properties. Since the ordinary physical properties base both the stresses and the strains on the original dimensions of the test piece, which are greatly changed during the test, they are essentially empirical values and do not represent physically either true stresses or true strains. Consequently, they do not give an accurate picture of the effects of different conditions, both mechanical and metallurgical, on the strength and ductility of the material. It is not, however, the purpose of this paper to review the various advantages accruing from the use of true stress and true strain values, since these have been shown elsewhere,1-l2 but to utilize them in representing the various effects considered. The true stress S and true strain (e = q') values mentioned above for the tension test are defined by1 S =1/A and where P, A, Ao are the axial load, the instantaneous area and the original area of cross section, respectively. From simultaneous readings of the axial load and the dimension or dimensions determining the instantaneous area of cross section, the true stress-strain curve is constructed by using the relations given in Eq. I. It is then the object of this paper to discuss the general effects of cold-rolling on the true stress and strain values for a low-carbon steel together with the effects of age-hardening and directionality on these properties. Preliminary Investigations The material considered throughout the paper is a low-carbon steel of the following chemical analysis: C, 0.19 per cent; S, 0.118; P, 0.092; Mn, 0.85; Si, 0.01. The stock was received in bars, 7 by 3/4 in., and was first annealed for one hour at 1650°F. followed by a furnace cool. Photomicrographs of this material showed considerable directionality even in the annealed condition. In view of the possible effects of the nonhomogeneity and directionality in this material, it was considered important to investigate their influence on the true stress-strain diagrams. In addition, the effect of strain-aging in this steel was also made the subject of a preliminary study. Effect of Aging on True Stress-strain Properties Since a certain time element would elapse between the cold-rolling operation and the final tension tests, it was determined to investigate the aging character-

Jan 1, 1945

By G. S. Jenkins

The statistics set forth by Professor Mitchell in a proceding paper very carefully brought out the points that indicate that a marked amount of consideration must be given to" the haulage problem to adapt it to local conditions as encountered. Professor Mitchell's paper showed a spread of from 10 tons per man to 50 tons per man on the production crews, which spread can be recognized as entirely too large when one considers that the product is being sold at a price within very close limits. While a portion of this spread may be explained by different methods in cost accounting as to what employees are applicable to the production crew, it cannot all be blamed on an accounting method. A good portion must be explained by the improper application of equipment to the needs incurred by the local conditions. It is in an endeavor to go into this phase that this paper is given. It will be necessary to qualify the points covered in order to keep the subject from becoming too wide in scope. Along this line, conditions will be only those involved in bituminous coal mine practices and only the haulage of coal that is loaded with mobile loading machines in seams 4 ft thick and better. Haulage Methods Employed The Consolidated Coal Co. (Illinois) has been operating on a modernized basis for about 20 yr. By modernized we mean the loading of coal with mobile loading equipment. In review of haulage methods, it must be remembered that the main line electric haulage locomotive has been in service for some 40 or jo years. To augment this main line haulage, the mule did a quite satisfactory job during hand-loading days, but was later replaced by the gathering locomotive, either battery or cable-reel operated. This type of haulage was the method in common use at the time the mechanical loading of coal became of major importance and the success or failure of loading machine installations may be largely accredited to haulage facilities in the early days; that is, in the period around 1930. The Consolidated Coal Co. had its struggle with this problem beginning in about 1927 or 1928. We were somewhat fortunate in that we were already using gathering locomotives powered by storage batteries at the time we introduced mechanical loading. This meant that we did not have to spend as much time training motormen and trip riders as many mines did that utilized only mules for their secondary haulage. This was all advantage, and our efforts could be focused on ways and means of providing adequate car service to the loading machine. Like most operations, we endeavored to gear the car service to the capacity of the machine, with a large crew endeavoring to load the maximum tonnage that the machine would handle. Toward that end our first move was to install switches

Jan 1, 1949

By Ronald C. Koo

THE effect of grain size on the mechanical properties of the bcc metals has been a subject of intensive theoretical and experimental study.'-l5 Quantitative relationships have been established experimentally between yield stress and grain size and between the ductile-brittle transition temperature and grain size in a number of metals.6"15 Much significance has therefore been attached theoretically to the grain size dependence. In all these experiments, different grain sizes were always achieved by annealing specimens at various temperatures. The implicit assumption was that any change in the dislocation substructure or in the distribution of impurities which might occur simultaneously with the production of various grain sizes had only a negligible effect on the mechanical properties. The validity of this assumption, however, is questionable. transformation in iron-nickel alloys is actually an extraneous phenomenon due to inadvertent compositional changes in the martensite if the heating rate is not sufficiently rapid. This complication can be avoided by up-quenching for the reversal treatment,5 and then the stabilization does not appear. Clearly, the lattice imperfections and strengthening produced by the reverse transformation are not responsible for the marked stabilization which has been observed by other investigators in these alloys. Data will be presented in this note to show that, at least in recrystallized tungsten of commercial purity, the difference in the ductile-brittle transition temperature of specimens annealed at various temperatures is more a result of a variation in the distribution of impurities rather than of the difference in grain size produced by the anneal. Ductile-brittle transition temperatures in tension were determined on powder-metallurgy tungsten specimens recrystallized at various temperatures. Tensile specimens having a gage length of 1.50 in. and gage diam of 0.18 in. were recrystallized at 1450°, 2000°, 2350°, 2550°, 2750°, or 2800" for 30 min in a vacuum furnace at a pressure of 1 x 10"5 mm of Hg and then tested at a constant extension rate of 8 x 10 per sec in an argon atmosphere from 100" to 800". Typical quantitative analyses of impurities are given in the Table. These results show that, within the precision of the analyses, see Table, annealing did not result in any detectable change in the impurity contents of the specimens, nor was there any detectable difference in purity between specimens having large differences in grain size annealed at the same temperatures . The results of the tensile tests yielded three distinct ductile-brittle transition curves approximately 225' apart. As shown in Fig. 1, data of specimens annealed at 1450°C and those of specimens annealed at 2000°C (O) fell on Curve A. Data of specimens annealed at 2350" and 2550°C fell on Curve B, and those of specimens annealed at 2750" and 2800°C fell on Curve C. The decrease in ductility with increase in annealing temperature became so pronounced that one third of the specimens annealed at 2750" and two thirds of the specimens

Jan 1, 1963

By R. H. Richman

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

Jan 1, 1963

By Willis R. Battles, William F. Cerini, P. H. Jones

A test for determining the plugging characteristics of an oil-well injection water has been developed. It consists in measuring changes of the filter rate of a water at constant pressure with cumulative throughput when passing the water through a medium grade sintered glass disk. Application of the test method was made to the water used in the Union Oil Company's experimental water flood of the Chapman zone in the Richfield field, Orange County, Callfornia. This water developed increasing plugging tendencies upon aging, even though the finished water from the plant filter exhibited few such characteristics. The plugging material was found to consist of calcium carbonate, ferric hydroxide, and organic substances that were presumed to be bacterial. Various method of stabilizing this water to prevent the formation of plugging material were attempted. Lowering the pH to approximately 6.4 by injecting carbon dioxide provided a moderately satisfactory means for stabilization but a better method of stabilizing this water was found to be first aging and then filtering. Introduction An experimental water-flood project was started on the Chapman zone of the Richfield field in March 1944 and has been described in a previous paper.' It consists of a single injection well drilled between old producing wells. A water-treating plant using primary alum flocculation, sedimentation and chlorination followed by secondary flocculation, sedimentation and fltration is employed to process the water before in@ion. In all of the water-treating operations, the system is open to the air, and no attempt is made to prevent the loss of carbon dioxide or absorption of oxygen by the water. The clear water is stored in a covered concrete basin and pumped through a Transite line to the suction of a high-pressure pump at the injection well' The high-pressure tubing in the well to the injection zone is cement lined. The untreated injection water is a mixture produced with the oil from the Chapman and Kraemer zones and is supplied from the disposal system. Because the injection well was relatively deep (injection zone about 3400 ft.) and would be expensive to replace, it was believed imperative to supply a nonplug-ging injection water and to develop laboratory procedures for evaluating the treated injection water with respect to its formation plugging properties. This report describes the development and application of the test procedure based on the assumption that the plugging properties could be determined by measuring the progressive decrease in flow rate of the water through a porous medium. If the quality of the injection water was good enough so that the plugging action on the porous medium was of small magnitude, it was reasoned that the tendency to impair flow in the formation would not be serious.

Jan 1, 1946

By Walter E. Duncan

The ores treated at the concentrating plant of the Mahoning Mining Co. at Rosiclare, Ill., come largely from the blanket replacement deposits of the northeastern part of Hardin County, Illinois, and consist of complex mixtures of galena, sphalerite and fluorspar in a gangue of quartz, limestone and sandstone. The several minerals are so intimately inter-grown that they are not liberated at the sizes usually treated by gravity concentration in the usual fluorspar plant. For this reason, an all-flotation method of concentration was developed in cooperation with the station of the U. S. Bureau of Mines at Rolla, Mo.1 This flotation separation made possible the commercial production of four coyentrates: (I) lead, (2) zinc, (3) acid-grade fluorspar and (4) metallurgical-grade Auorspar.2-3 Although fluorspar had been floated in Canada in 19214 and a plant at Rosiclare had been floating fluorspar since March 1929, fluorspar flotation was given considerable impetus by the Mahoning developments, since some features of the separation were quickly adopted by other fluorspar companies. The Bureau of Alines5 reports that in the 10 years preceding 1938 only 50,552 tons of fluorspar flotation concentrates were produced in the United States. The rise from this almost nominal figure to 153,750 tons (largely acid grade) in one year (1944)6 is indicative of the activity in fluorspar flotation occasioned by the war. The industry thus proved to be in a position to expand and keep up reasonably well with the requirements imposed upon it by such developments as occurred in high octane aviation gasoline alkylation, in the use of Freon as a refrigerant and as carrier in the Aerosol "bug bomb," and in the atomic bomb project as well as in the expansion of other activities requiring hydrofluoric acid; for example, the aluminum industry. Despite the fact that the greater portion of acid-grade fluorspar produced in the last few years went directly into war uses, the future of the acid-grade field still appears bright. As a result of the activity in fluorine chemistry during the war, it seems likely that in the relatively near future almost every phase of human endeavor will find some fluorine compound involved. The other three concentrates produced deserve some attention in these introductory remarks. The lead concentrates first produced contained both zinc and fluorspar but these did not interfere with their marketing. As will be pointed out later, the quality has steadily improved until today it is a relatively high-grade product. Although some zinc smelters accept concentrates containing limited quantities of fluorspar, it is a very objectionable impurity. Since flotation methods fail in the complete removal of the fluorspar, chemical methods were developed for

Jan 1, 1948

By H. L. Luo

SYSTEMATIC investigations of the Fe-Ga system have been reported only very recently."' The maximum solid solubility of gallium in a-Fe is nearly 50 at. pet at 900°C. However, from Ref. 1, it was not evident that the a-Fe solid solution could be retained successfully beyond 17.38 at. pet Ga by solid-state quenching. The present investigation reports the retention of a-Fe solid solution at 50 at. pet Ga by quenching from the liquid. An ordered phase of CsC1-type B2) structure was observed between 34 - 50 at. pet Ga. Since it was considered very probable that the CsCl structure would occur at high temperatures, alloy filings were also quenched by the conventional quenching technique. In addition to the CsCl phase, a second ordered phase of BiF3-type (DO3) structure was found in the range 25 - 30 at. pet Ga. Alloys were prepared from elements of 99.99 pet purity or better, induction-melted in alumina crucibles under hydrogen. After reweighing, the alloy ingots were cast into wires under argon. From the weight losses and the reproducibility of the lattice parameters, compositions were estimated to be within ± 0.3 at. pet. The techniques of quenching from the liquid state were reported before.3-5 Prior to quenching, a small section of cast alloy wire (30 - 50 mg) was melted in an alumina insert under an argon flow. The quenched specimens were in the form of flakes, typically 1 sq mm in area. For solid-state quenching, alloy filings passing 200 mesh were sealed under a reduced helium atmosphere in a thin-bottom silica tube. After heating for -30 min at the desired temperature in a vertical furnace, the sealed tube was rapidly dropped into ice water so that the thin bottom of the tube broke on impact. The quenched alloy filings were always ferromagnetic and could be collected by a magnet. X-ray diffraction patterns were taken with iron-filtered cobalt radiation in a 114.6-mm-diam Debye-Scherrer camera. High-angle lines were always resolved and spacings were computed relative to ? (CoKa1) = 1.78890Å. Lattice parameters were obtained from extrapolation against the Nelson-Riley function. The variation of lattice parameter with composition is shown in Fig. 1, together with the data of Dasarathy and Hume-Rothery.1 Uncertainties in the present measurements are within the dimensions of the symbols or indicated by error bars. X-ray diffraction lines indicative of CsC1-type ordering could be clearly identified for alloys of 34 - 50 at. pet Ga quenched from the liquid and alloys of 35 - 41 at. pet Ga quenched from -975°C. Within experimental error, no difference in

Jan 1, 1968

By W. W. Smeltzer

The linear formation rates of wustite films have been determined over the temperature range 590° to 1030°C using a vacuum microbalance technique. These rates are dependent directly on the partial pressure of carbon dioxide, Activation energies for film and scale formation in carbon dioxide and oxygen atmospheres are equivalent to either the dissociation energies of carbon dioxide and oxygen, or the activation energy for the diffusion of cation vacancies in wustite. Of the metals, iron is the most widely used basic constituent of durable alloys despite its intrinsic property of converting at a relatively rapid rate to the oxides from which it is derived. This property has accounted partially for many investigations on the oxidation of iron at low and high temperatures. Interpretation of the results have been complicated by formation of multilayers containing the various oxide phases. To aid in elucidation of the oxidation kinetics, measurements have been carried out in this investigation on the growth of the wustite surface layer. There are several studies directly related to the objective of this investigation. The growth of multilayer scales has been demonstrated to be diffusion controlled in oxygen at atmospheric pressure over the temperature range 450" to 1200°C by Davies, Simnad, and Birchenall.' To gain an insight into the diffusion mechanism, Himmel, Mehl, and ~irchenall' determined the self-diffusion coefficients of iron in wustite, magnetite, and hematite. These results were used to evaluate the oxidation rates of iron and its oxides, taking as a basis the theoretical parabolic rate equation developed by Wagner., The evaluations were compared to experimental data and were shown to provide essential confirmation of this theory. Fischbeck, Neundeubel, and salzer4 have demonstrated that the oxidation of iron in carbon dioxide and other atmospheres at high temperature obeys a linear relationship. Because the Arrhenius temperature coefficients of the reaction rate constants changed at the A, point they concluded that the passage of iron into the oxide controlled the reaction. This viewpoint has been accepted by Benard and ~albot' to explain the occurrence of linear rates in oxygen before the onset of diffusion-controlled parabolic oxidation. This basic premise of a rate-controlling reaction at the iron/oxide interface has been questioned recently by Hauffe and Pfeiffer.' Since the formation of wustite may follow a linear or parabolic relationship depending on the pressure of the gaseous re-actant, they propose that linear oxidation is determined by a chemisorption reaction while parabolic oxidation is controlled by diffusion. As confirmation of this viewpoint, Hauffe and pfeiffer6 and Pfeiffer and ~aubmeyer' have established that the linear scaling constants of wustite formation at 1000°C in carbon-dioxide or low-pressure oxygen atmospheres

Jan 1, 1961

By William F. Cerini, Willis R. Battles, P. H. Jones

A test for determining the plugging characteristics of an oil-well injection water has been developed. It consists in measuring changes of the filter rate of a water at constant pressure with cumulative throughput when passing the water through a medium grade sintered glass disk. Application of the test method was made to the water used in the Union Oil Company's experimental water flood of the Chapman zone in the Richfield field, Orange County, Callfornia. This water developed increasing plugging tendencies upon aging, even though the finished water from the plant filter exhibited few such characteristics. The plugging material was found to consist of calcium carbonate, ferric hydroxide, and organic substances that were presumed to be bacterial. Various method of stabilizing this water to prevent the formation of plugging material were attempted. Lowering the pH to approximately 6.4 by injecting carbon dioxide provided a moderately satisfactory means for stabilization but a better method of stabilizing this water was found to be first aging and then filtering. Introduction An experimental water-flood project was started on the Chapman zone of the Richfield field in March 1944 and has been described in a previous paper.' It consists of a single injection well drilled between old producing wells. A water-treating plant using primary alum flocculation, sedimentation and chlorination followed by secondary flocculation, sedimentation and fltration is employed to process the water before in@ion. In all of the water-treating operations, the system is open to the air, and no attempt is made to prevent the loss of carbon dioxide or absorption of oxygen by the water. The clear water is stored in a covered concrete basin and pumped through a Transite line to the suction of a high-pressure pump at the injection well' The high-pressure tubing in the well to the injection zone is cement lined. The untreated injection water is a mixture produced with the oil from the Chapman and Kraemer zones and is supplied from the disposal system. Because the injection well was relatively deep (injection zone about 3400 ft.) and would be expensive to replace, it was believed imperative to supply a nonplug-ging injection water and to develop laboratory procedures for evaluating the treated injection water with respect to its formation plugging properties. This report describes the development and application of the test procedure based on the assumption that the plugging properties could be determined by measuring the progressive decrease in flow rate of the water through a porous medium. If the quality of the injection water was good enough so that the plugging action on the porous medium was of small magnitude, it was reasoned that the tendency to impair flow in the formation would not be serious.

Jan 1, 1946

By Walter E. Duncan

The ores treated at the concentrating plant of the Mahoning Mining Co. at Rosiclare, Ill., come largely from the blanket replacement deposits of the northeastern part of Hardin County, Illinois, and consist of complex mixtures of galena, sphalerite and fluorspar in a gangue of quartz, limestone and sandstone. The several minerals are so intimately inter-grown that they are not liberated at the sizes usually treated by gravity concentration in the usual fluorspar plant. For this reason, an all-flotation method of concentration was developed in cooperation with the station of the U. S. Bureau of Mines at Rolla, Mo.1 This flotation separation made possible the commercial production of four coyentrates: (I) lead, (2) zinc, (3) acid-grade fluorspar and (4) metallurgical-grade Auorspar.2-3 Although fluorspar had been floated in Canada in 19214 and a plant at Rosiclare had been floating fluorspar since March 1929, fluorspar flotation was given considerable impetus by the Mahoning developments, since some features of the separation were quickly adopted by other fluorspar companies. The Bureau of Alines5 reports that in the 10 years preceding 1938 only 50,552 tons of fluorspar flotation concentrates were produced in the United States. The rise from this almost nominal figure to 153,750 tons (largely acid grade) in one year (1944)6 is indicative of the activity in fluorspar flotation occasioned by the war. The industry thus proved to be in a position to expand and keep up reasonably well with the requirements imposed upon it by such developments as occurred in high octane aviation gasoline alkylation, in the use of Freon as a refrigerant and as carrier in the Aerosol "bug bomb," and in the atomic bomb project as well as in the expansion of other activities requiring hydrofluoric acid; for example, the aluminum industry. Despite the fact that the greater portion of acid-grade fluorspar produced in the last few years went directly into war uses, the future of the acid-grade field still appears bright. As a result of the activity in fluorine chemistry during the war, it seems likely that in the relatively near future almost every phase of human endeavor will find some fluorine compound involved. The other three concentrates produced deserve some attention in these introductory remarks. The lead concentrates first produced contained both zinc and fluorspar but these did not interfere with their marketing. As will be pointed out later, the quality has steadily improved until today it is a relatively high-grade product. Although some zinc smelters accept concentrates containing limited quantities of fluorspar, it is a very objectionable impurity. Since flotation methods fail in the complete removal of the fluorspar, chemical methods were developed for

Jan 1, 1948

By R. W. Gurry

IN the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and 1110°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon content of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched. The mean result of concordant measurements is that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C. (1755°F.) and 1.89 per cent at 1110°C. (2030°°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutectoid temperature (738°C. or 1360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature1135°C. (2095°F.) instead of the commonly accepted value of about 1.7 per cent. EXPERIMENTAL PROCEDURE The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.1 In the empty furnace the range of temperature over a distance of 4 cm, at the heat center was 9°C. (16°F.) but at a given location the temperature remained within ±0.5°C. (0.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (1760°F.) and 1110°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with

Jan 1, 1942

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

THERE has been a recent revival of interest in the intermetallic compound AgMg as an experimental material for study of the physical and chemical properties of simple ordered structures. Studies of mechanical behaviors,1-4 diffusion,5,6 and thermo-dynamic properties7'8 have been reported. In several of these studies, heat treatments have been carried out in argon-filled silica capsules at temperatures as high as 750°C with no apparent adverse effects. The present authors were, therefore, startled to discover in the course of some yet unpublished work, that gross melting of near-stoichio-metric AgMg compositions occurred in such samples more than 100 deg below their melting point of about 800°C. This note is to report a brief series of experiments carried out to establish the reason for this behavior. Gross errors in sample composition and failure of furnace temperature controls were quickly eliminated as causes of melting. The first tangible lead came from chemical analysis of an AgMg sample which had melted during treatment at 750°C. A silicon content of 3.3 wt pct was found. Since satisfactory analyses had been obtained on the original as-cast ingot, contamination by diffusion and/or reaction with the fused silica capsule seemed a distinct possibility. A perplexing fact, however, was the apparently capricious incidence of the effect. Not only was it previously unknown, even in the experience of the present authors; but, in the early part of the present study, melting sometimes occurred and sometimes not with specimens treated under constant conditions. Indeed, one sample successfully survived a 750°C heat treatment and yet melted completely during the course of a subsequent anneal in an identical capsule at a lower temperature. To obtain evidence that silicon contamination could lower the melting point to the extent observed, the following experiment was performed. A series of ternary alloys was made up with a stoichiometric AgMg base and containing 0.1, 0.2, 0.4, 1, 2, and 4 wt pct Si. Melting was done in MgO crucibles under a cover of argon gas. After holding 10 to 20 min in the temperature range 850° to 900°C, the alloys were allowed to solidify in the crucible and the temperature during cooling automatically recorded with a Pt/Pt-10 Rh thermocouple. Results from the cooling curves are shown in Fig. 1. Checks within 2 to 5C° were obtained upon repeated melting, cooling, and freezing. The whole series of cooling curves as well as metallographic examination of the melted alloys established that the AgMg rich portion of the AgMg-Si quasibinary is an eutectic-type system. The melting point of AgMg is lowered from approximately 820°C in the pure stoichiometric binary9 to about 710°C in the saturated intermetallic phase. Since second phase was observed in all samples on cooling to room temperature, the solid solubility of AgMg for silicon evidently falls rapidly with decreasing temperature as indicated schematically by the dashed solvus in Fig. 1. It is thus established that a silicon content

Jan 1, 1963

By Walter Bonsack

THE CHAIRMAN.-This is the third and last session of the Institute of Metals Division's Symposium on Secondary Metals, and certainly the best of those that I have attended in the last few years. I would say that the increase in interest in secondary metals is quite noticeable by the steadily increasing attendance at these meetings. We have heard about the necessity of utilizing salvaged materials, but we still speak about them as low-grade, or down-graded materials. We still have the wrong perspective. We must willingly admit that these materials are valuable; we cannot go on using the choicest primary metals as morsels for our economic diet in a war of such unbelievable dimensions. This brings up the question-why are we so selective. The answer certainly is not that we know nothing else will do, but rather that we do not know what else will do. To be honest, we should admit our lack of knowledge concerning our complex alloys. Compared to the organic chemists, we metallurgists are very conservative, and the sooner we realize this and start to overcome it the better, because if we do not eliminate this difference, many customers of the metals business will go over to the plastics. If we take for example the development of aluminum alloys, you will see what I mean. From the binary aluminum alloys of 1920, we have progressed to ternary and quarternary alloys in the 1930's. We are only now beginning to use more complex alloys as we are forced to learn more about the effect of various elements on existing alloys. The effects of these elements should be studied now. They can be studied by two methods of approach. The usual method is to start from the base alloy and add various elements one by one in increasing amounts and study the resultant changes in properties. This is a tedious, long way. The other method which the smelters frequently use is to take the off-grade heats and study their characteristics. While the producer of primary alloys often has difficulties in alloying certain elements with the alloy under investigation, the smelter often finds them well alloyed in his raw materials and has no difficulties at all. Elements such as lead are difficult to alloy with aluminum and they tend to segregate severely. However, the amount which will remain alloyed in the metal is usually found in some "secondary" aluminum alloys. If one considers such concentration as the saturation, then by dilution with the same type of alloy, but free of such element, one can produce numerous intermediary alloys for investigation. In this fashion one is fairly certain to get uniformly spaced concentrations of the element under investigation. Similar cases probably exist with other metals. Nevertheless, the amount of work necessary to study all possible combinations is still tremendous. Necessity forces us now to utilize alloys which contain more elements than we are accustomed to. It is, therefore, necessary to study carefully the more complicated alloys. In secondary aluminum we are working and using the alloys which contain as many as 6 to 10 elements and we have learned over a period of several decades to balance

Jan 1, 1943

By Robert M. Dreyer

Although lateritic ore deposits are relatively flat-lying, surficial ore bodies, the evaluation of lateritic bauxite and nickel deposits is among the most difficult problems confronting an economic geologist. Laterite is a soil formed under tropical conditions resulting in the concentration, within the soil zone, of certain trivalent metals - principally iron and aluminum, but also, locally, nickel and manganese. The soil zone is divided into two parts: (a) the true soil or lateritic zone and (b) the zone of partially altered bed rock or saprolite. Whereas bauxite generally is confined to the lateritic zone, some nickel deposits occur in both the laterite and saprolite zones. The evaluation of bauxite and lateritic nickel deposits thus has both similarities and differences. These ores have been formed by supergene, soil-forming solutions moving downward through zones of widely varying permeability within the weathering rock. Because the permeability varies widely, both vertically and laterally. the extent of weathering may vary greatly within short distances. Because the weathering process varies widely, the degree of metal concentration may also vary widely. It is not at all uncommon for a laterite to change, within a few centimeters, from a virtually valueless rock to a high grade ore. Moreover, the depth of weathering, and hence the depth and form of the ore profile, vary greatly. Obviously, for this type of deposit, a few grab samples or a few drill holes are virtually worthless. The evaluation of such a deposit requires a sophisticated statistical study based on thousands of carefully selected samples. As a rule of thumb, the cost of evaluating a large bauxite or lateritic nickel deposit will be about one cent per ton of ore in the ground. Thus, the cost of evaluating a several hundred million ton deposit may be considerable. The following factors must be considered during the evaluation: Type of Sampling: The best and most reliable samples for the evaluation of lateritic ores are taken along large, vertical channels in hand-dug pits. Where labor costs are high, some form of drilling may be used in place of pitting, but it is always wise to choose a drilling procedure after checking drilling results against a series of pit channel samples. The drilling may not reproduce exactly the results from pit channel samples, but it may be possible to derive a constant correction factor. If the physical character of the laterite varies within the deposit, it may, of course, be necessary to change the type of drilling, the correction factor or both. In some areas, it has been found empirically that augers, chum drills, vacuum drills, rotary drills, or core drills yield satisfactory results. The problem is to find which drilling technique gives results most similar to channel samples through the heterogeneous sequence characterizing the laterite in a given area. In lateritic nickel deposits, the drilling characteristics of the lateritic and saprolitic portions of the deposit are very different. Within the saprolite, the major nickel values are commonly found in weathered zones within less altered boulders - a type of occurrence which makes sampling very difficult.

Jan 1, 1979

By H. Foster Bain

THIS subject is one that has attracted my attention for a good many years. All of us have had occa-sion to think of the waste that comes from the poor organization of our methods of finding mines and of looking after prospects. Probably all of us, in, examination work, have made a long and difficult journey to see some prospect, in a far country, or often in the mountains, have found the prospect one that never could be developed, and have learned for the first time that it had been previously examined by from two to six of our professional associates, who, each in turn, condemned the property as worthless. I know properties, as all of you do, that have been repeatedly examined by first-class engineers. Perhaps it would not be safe or wise to have an invariable rule that, each prospect should be entitled to only one examination by one engineer; and yet, it seems to me that somewhere there is a middle ground to take; it is hardly necessary that each little prospect should be examined so many times that the walls get greasy from the climbing of mining engineers, or the stopes get filled up with cigarette stumps. 'This mining engineering profession ought to have brains enough to find some way of making this unnecessary, and of making the benefit of an examination, in some cases at least, and in a much larger number of cases than at present, avail-able to the industry as a whole. If we would save the amount of money that is spent unnecessarily on reexamination of properties, and let that money flow into the actual development of )properties, I believe that, in the long run, we would be better off. Just how to do that is another problem. In 1916, while in London, Edgar Rickard and I attempted to do something of that kind. We started to organize a plan whereby mining engineers might, with the consent of their class, turn over to a central organization their reports on properties they had examined, whereby men who had occasion to look up these same properties might, on payment of a fee (which should go back to the original client, if you desire, or might be devoted to some other purpose for the benefit of the industry), have access to these earlier reports. We found, in the short time we considered this matter, that a good many British engineers, and a good many of the companies, were willing to consider this. In other words, they were willing to pool their information, as a matter of practical experience. We all know the enormous value of pooling information. I think it is a problem that may well be considered from the point of view of the industry as a whole, which the Society might attempt' to work out on a businesslike basis. Assuming, however, that it is possible to work out a plan whereby we get the minimum number of examina-tions that are necessary and we make some saving in money, we reach another stage-the problem of the examination itself.

Jan 3, 1922