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By C. B. Alcock, M. G. Hocking

The kinetics of the growth of sulfate layers on blocks of Cu20 has been studied between 688" and 800°C. At 788c the over-all weight increases followed the parabolic rate law, with k = 216 30 sq mg per cm4 min, using a 1:1 entering gas mixture of SO2:02. At 757 after an initial linear period the parabolic rate law was followed, with k = 57.8 10 sq mg per cm4 min. The gas mixture required a platinum catalyst to produce the maximum SOs pressure. The sulfation rate at 757' and 788c was high until all the CUZO had changed into a core of CuO, when it became very much lower. At 757°C marker experiments showed that the sulfates (CuO. CuS04 and CuSO4) grow outwards from the oxide surface, but CuO. CuS04 mixed with CuO was found beneath the markers. At 688 markers were found at the CuO. CuS04/CuS04 interface. Visual observations at 757 showed a liquid eutectic moving beneath the sulfate surface. causing very rapid sulfation and extruding to solidify as thick 'needles" up to 8 mm long. Marker experiments have shown conclusi.cely that CuO grows on Cu20 in air by the outward migration of copper. ThermODYNAMIC measurements on the sulfate and basic sulfate of copper, reported recently,' are followed here by measurements of the rates of formation of these sulfates on cuprous oxide, in order to provide a background for the understanding of roasting processes. peretti2 and McCabe and Morgan3 have shown that the phase Cu20 lies next to Cu2S when the sulfide is roasted under conditions where sulfates will be formed. Since this would present too complex a system for kinetic study, the present work4 has been based on the kinetics of sulfation of the oxide phase. The results of a study of the kinetics and mechanism of the sulfation of cobaltous oxide have recently been reported.4,5 Results on the sulfation of cuprous oxide have also appeared,6 but are at variance with those to be reported here. This seems to be because the previous workers6 did not obtain constant SO3 pressures from the SO2/O2 sulfating gas mixtures used, as will be discussed later. Wadsworth, Leiter, Porter, and Lewis found that the sulfates produced when SO2/O2 mixtures are passed over Cu20 at red heats are CuS04 and the basic sulfate CuO.CuSO4. When the decomposition of CuS04 was followed' by differential thermal analysis, a stage corresponding to CuO .CuS04 was reached before decomposition into the oxide occurred. APPARATUS The vertical furnace used for quantitative studies was a conventional resistance-heated and propor- tionately controlled furnace with an even zone (1 deg) which was 4 cm long. The gas mixtures of SO2 and 02 were made by mixing measured flows from capillary flowmeters and drying over phosphorous pentoxide before passing them into the Pyrex top-piece of the furnace assembly. A mullite tube of bore 2% cm was used as reaction vessel and at the bottom of this tube was a trap for SO3, which condensed as a colorless liquid. The residual gas was led into a fume cupboard for ventilation to the atmosphere. The furnace used for visual observations of needle growth and other phenomena consisted of a transparent silica reaction tube of bore 3 cm, having an optically flat silica window sealed into its wall. The reaction tube was clamped vertically, inside a mullite tube of bore 4 cm and length 42 cm which was heated by Kanthal windings. The window in the silica reaction tube was arranged opposite a hole 3 cm wide and 2 cm tall which had been cut in the wall of the mullite winding tube 19 cm from its top end. A binocular microscope was used to look through the window, illumination being provided by a focusing microscope-lamp offset sideways and downwards. The oxide block to be sulfated was suspended from the removable Pyrex top-piece to the reaction tube, by means of which it was inserted at the start of the experiment, and through which entered the S02/02 gas mixture. The variation of the temperature inside the reaction tube with horizontal and vertical displacement from the window was investigated, and, while it can be said that the temperature was constant 1 deg, its value at a given position was known only to 12 deg. In both furnaces, the oxide block to be sulfated was suspended from a small silica hook immediately downstream from a platinum thimble used as catalyst, which was held on a long silica rod from a Pyrex spring attached to the removable Pyrex top-piece of the furnace. The spring was only included in the quantitative sulfating furnace; its sensitivity was 1.4 cm per g and it was found to be free from creep in a 16-hr test when carrying the working load. The extensions were followed by a cathetometer which could be read to 0.001 cm, corresponding to i0.7 mg. Extensions of the spring were measured on adding weights between 5 and 500 mg to the working load (thimble + oxide block), and Hooke's law was closely obeyed. SAMPLES Cuprous oxide blocks were prepared by oxidizing Johnson Matthey "Specpure" copper sheet of 1 mm thickness (impurities: iron at 3 ppm, silver at 2 ppm, lead, nickel, sodium, and silicon each at 1 ppm, calcium, chromium, magnesium, and manganese each at less than 1 ppm) for 6 days in air at 1000°C in a re-crystallized alumina boat. It has been reported7 that when Cu20 is prepared by heating copper sheet for 1 day the central plane of the blocks produced consists

Jan 1, 1967

By George R. Ensminger, E. Heaton Hemingway

During the past year, the Watertown Arsenal has been interested in the occluded gas and oxide content of certain ordnance steels in order to determine, if possible, whether some of the peculiar failures in their physical properties might not be traced to these causes. For the purpose of best accomplishing a study of this nature, it was decided to heat the various samples of steel in a vacuum for definite periods of time at high temperatures and carefully examine the quantity and composition of the gases evolved. By the use of a fused quartz tube fitted with a water-cooled, ground-glass stopper, it was possible to maintain a vacuum at a temperature of 1000" C. for 10 hr. without perceptible leakage being evidenced as measured by a McLeod gage. The silica tube was connected with an evacuating system so constructed that the volatilized gases could be removed from time to time and a low vacuum of 0.0002 to 0.0010 mm. of mercury continuously maintained. At no time during the period of heating or in the removal of the gases did the evacuated system come in contact with rubber stoppers or any rubber connections, making contamination from such a source, impossible. In other words, the only volatile products that could be: obtained must necessarily have come from the steel itself or from the glass and fused quartz system or from the mercury used as a sealing agent. In the carlier experiments, the steel treated was in the form of turnings, but this practice was discarded because the weight's of the turnings before and after being heated were widely inconsistent,, even when taken from the same piece of steel. This discrepancy developed largely through variation in the amount of metal volatilized with the gases; this metal could always be seen in the form of a ring where it condensed in the cooler portion of the tube in either the amorphous or crystalline condition. Because of the frequency in occurrence and the variation in the manner of deposition, this material was roughly analyzed and found to consist for the most part of iron. At the same time two samples of steel that had been

Jan 1, 1922

By E. Heaton Hemingway, George R. Ensminger

During the past year, the Watertown Arsenal has been interested in the occluded gas and oxide content of certain ordnance steels in order to determine, if possible, whether some of the peculiar failures in their physical properties might not be traced to these causes. For the purpose of best accomplishing a study of this nature, it was decided to heat the various samples of steel in a vacuum for definite periods of time at high temperatures and carefully examine the quantity and composition of the gases evolved. By the use of a fused quartz tube fitted with a water-cooled, ground-glass stopper, it was possible to maintain a vacuum at a temperature of 1000" C. for 10 hr. without perceptible leakage being evidenced as measured by a McLeod gage. The silica tube was connected with an evacuating system so constructed that the volatilized gases could be removed from time to time and a low vacuum of 0.0002 to 0.0010 mm. of mercury continuously maintained. At no time during the period of heating or in the removal of the gases did the evacuated system come in contact with rubber stoppers or any rubber connections, making contamination from such a source, impossible. In other words, the only volatile products that could be: obtained must necessarily have come from the steel itself or from the glass and fused quartz system or from the mercury used as a sealing agent. In the carlier experiments, the steel treated was in the form of turnings, but this practice was discarded because the weight's of the turnings before and after being heated were widely inconsistent,, even when taken from the same piece of steel. This discrepancy developed largely through variation in the amount of metal volatilized with the gases; this metal could always be seen in the form of a ring where it condensed in the cooler portion of the tube in either the amorphous or crystalline condition. Because of the frequency in occurrence and the variation in the manner of deposition, this material was roughly analyzed and found to consist for the most part of iron. At the same time two samples of steel that had been

Jan 1, 1922

By A. Keil

TO measure the absolute conductivity of metallic specimens it is generally necessary to have exact geometrical shapes and good electrical contact with the test-piece. To overcome limitations of the standard methods, an electronic conductivity-meter* Trade name, Sigmatest; model Dr. F. Forster; Reutlingen, Ger-many. has been developed, which works on the principle of inducing high frequency eddy-currents in the specimens and measuring the reaction of these curients on a measuring coil.',' To attach the instrument to the test specimen, a flat area of about 10 mm diam is all that is necessary. The reading is taken off a scale calibrated in pet of International Annealed Copper Standard. The induced eddy-currents are propagated in a circular motion parallel to the surface. Thickness of the layer included in a measurement depends on the frequency used. With a frequency of 60 kc per sec, the penetration of the currents was 0.8 mm at the upper limit of the scale, and 2 mm at the lower limit. The method is limited to nonferrous metals and other applications have been described elsewhere." The object of the present investigation was to detect the formation and growth of surface layers of differing conductivity, and to determine the depth to which these changes could be observed. A well known phenomenon which illustrates the problem is the internal oxidation of certain silver alloys containing base metal solutes, such as copper or cadmium, when they are annealed in an oxidizing atmosphere.4, 5 Until now, the only methods available for following these phenomenon have been metallo-graphic examination and hardness tests.0, 7 Changes in mechanical properties of copper alloys by internal oxidation were recently discussed in a more general way by Martin and Smith." When measuring these conductivity changes it must be remembered that the only absolute values of conductivity are those of 1) the nontreated homogeneous specimen, and 2) the final values obtained with a surface layer of depth comparable to the penetration of the eddy-currents. All intermediate values refer to the mixed conductivities of the transformed surface layer and the untransformed alloy, and are thus readings of relative value only. Experimental Results Specimens were annealed for 1/2 hr at 800°C in hydrogen, and the internal oxidation was carried out by thermal treatment in air at 800°C. Fig. 1 shows the results of the first series of experiments. With internal oxidation of a solid solution of 8 pet Cd in silver, the conductivity rises continuously until the surface layer formed has become thick enough to be the deciding factor (about 400µ). Precipitates of CdO are mainly in the form of points, Fig. 2, and, as a result, the electric contact between the silver crystals is not distorted by them. Brine11 tests were run with a 1.25 mm ball and a 7.812 kg load. The specimen annealed in hydrogen and oxidized to a depth of 400µ had a hardness of 40 Bhn,

Jan 1, 1959

By J. Ruzicka

IN creep testing, material is subjected to a constant load, preferably at a constant temperature, and its rate of deformation is measured. The method of loading can be of various types but in this paper only creep testing under tensile load will be considered. The ordinary tensile test is essentially a comparison test in conditions that frequently bear little or no relation to those under which the test material is to be used in service. The purpose of creep tests is to measure the strength of the test material at slow rates of deformation that more nearly approach the rates realized in service. One purpose of this paper is to illustrate that the creep test, in addi-tion to its value as a service test, is superior to the ordinary tensile test as a sensitive tool for the comparison of certain metals in investigative testing. The other purpose is to describe equipment having distinctive features of design that make it especially suitable for such tests. Representative data obtained with this equipment on a group of rolled zinc-base materials are given. These data are compared with those from practical comparison tests of the creep type on weatherstrip fabri-cated from the same group of materials. The comparison illustrates the value of the fast creep test and of the equipment.

Jan 1, 1937

By M. L. Fuller

MOST commercial alloys undergo changes in phase composition after casting. This is a natural result of the fact that the alloys are not in a state of phase equilibrium as cast and phase changes will therefore take place, with more or less rapidity, in an attempt to attain equilibrium. The practical aspect of aging in zinc-alloy die castings concerns the changes in physical properties and in dimensions that may accompany aging phase changes. Harmful alterations have been reduced to a minimum and zinc-alloy die castings are being produced today that are so stable with respect to dimensions and physical properties that they are entirely suitable for most practical purposes1. In the first paper2 of this series, and in this paper, aging phase changes of zinc alloy die castings have been investigated and the possible influence of these changes on dimensional changes of the castings has been evalu-ated and compared with the dimensional changes actually experienced. The change of dimensions has been selected for practical comparison in these papers because the effect of phase changes on the dimensions of a casting is directly calculable; from X-ray crystal-analysis data of the phase structure. The die-casting alloys considered contain, in addition to zinc, 4 per cent of aluminum, about 0:03 per cent magnesium, and from 0 to 3 per cent of copper. It was shown in the former paper that the eutectoidal decomposition of the beta aluminum-zinc phase, while intrinsically capable of causing a considerable shrinkage, can have very little effect on the observed shrinkage of die castings because it takes place within a few days of aging, whereas the observed shrinkage continues for five weeks. It was therefore concluded that the other existing phase change,

Jan 1, 1935

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Jan 1, 1938

By Arthur Lubinski, K. A. Blenkarn

It is explained why the bottom portion of freely suspended tubing in a pumping well buckles and straightens in succession during the pumping cycle. Field evidence of resulting rod-on-tubing wear, excessive polished rod load, and excessive horsepower are given. The possibility that buckling hastens pump wear is strongly suggested. Means for either prevention of buckling or for mini-mizing its effects are explained, their relative merits compared, and field results of their use given. These means are: tension anchors, tail pipe, sucker rod guides, and corrosion inhibitors. Charts and formulas for best use of tension anchors, tail pipe, and guides are given. Use of tension anchors, or compression anchors with a heavy tail pipe, prevents both buckling and breathing, thus improving volumetric efficiency. Without tail pipe, buckling above compression anchors precludes such improvement. INTRODUCTION It is well known that a column must be subjected to some compression in order to buckle; and also that a structural member does not buckle if subjected to a tension. When consideration is given to a tubular column, the question may be asked, "How is the buckling phenomenon affected by inside or outside pressure?' At first, it seemingly should not be affected. However, this is not so. In order to arrive at a correct deduction one should first understand the basic reasons for buckling of a column under loading*. Then he should add to the effect of that loading the effect of pressure. Following this procedure, one may discover quite unexpected phenomena. In some cases, when subjected to more pressure inside than outside, a pipe may buckle under tension. In other cases, a pipe may remain straight, although subjected to a very large compression. In 1950 and 1951 it was explained why the bottom portion of a string of pipe freely suspended in a well does not buckle even when subjected to a large compression due to buoy- ancy.2,3 It was shown that the com-monly used concept of a neutral point, as being a point in the string with neither compression nor tension, is inadequate, and a more relevant definition of the neutral point was introduced. The findings were also generalized to cases of different pressures inside and outside a pipe.3a Later, in a further generalization, allowance was made for variations of stress and pressure with depth.' The findings were applied to the new technique of hydrostatic high pressure testing of lengths of pipe in the mill.5 In 1952 it was observed that previous theoretical findings apply to tubing in pumping wells. The lower part of freely suspended tubing buckles during the upstroke portion of the pumping cycle. Later, it was ascertained that this phenomenon is responsible for wear and malfunctioning of the equipment. Various remedial measures were devised and successful field trials conducted. Only brief mentions on the subject have been published.6,7 In this paper, the phenomenon of tubing buckling is explained, field

Jan 1, 1958

By Simon D. Strauss

Production and consumption of nonferrous metals in the United States during 1950 were at peak levels for the postwar period, as is shown in Tables I, II, and III. The trend of production was upward through most of the year. At the year end, with the possible exception of the Tri-State zinc-lead district, the large mining operations in the country were running at capacity. The absence of serious labor interruptions during the year was an important contributing factor in the increased out-put of metals, since in each of the previous postwar years there had been a number of major strikes which affected production adversely.

Jan 2, 1951

By C. Dirksen

This study investigates whether oxygen consumption during segregated forward combustion may be affected by natural convection. Linear theory indicates that thermal instability occurs in a horizontal porous medium when the modified Rayleigh number N 'Ra exceeds a critical value of about 40. Most experimental results, including those described here, indicate this value to be about an order of magnitude smaller. N ', is derived from "differential similarity" and the proper time scale factor is also obtained. The critical value of N'ra for a horizontal, water-saturated porous medium at atmospheric pressure subjected to a uertical temperature gradient was found to be about 3.0. The ambiguity in the value of N'R, arising when fluid properties cannot be assumed constant is indicated. Natural convection was observed for oblique systems below N 'Ra , while simultaneous horizontal flow did not affect N Racrit. The expected range of values for the various parameters pertaining to segregated forward combustion is indicated and the corresponding values of N 'Ra calculated. Only under very favorable conditions, such as high permeability, high pressure and low top temperature, can the critical value of N 'R, be exceeded. Thickness of the convection layer should not become too large, since the time required to obtain significant mixing is proportional to the square of the thickness. For an oblique combustion frant the conditions for significant mixing may be less strenuous. LNTRODUCTION Laboratory1,2 and field314 experiments have shown that a markedly upgraded oil can be produced by in situ forward combustion. Under certain conditions injected air may move through a high permeability, gas-saturated channel over the oil-saturated layer, while combustion takes place, exclusively, at the horizontal interface (Fig. 1). Such a channel may be a natural gas cap, or it may result from a forward combustion process in which injected air and combustion gases fingered through the top of the formation, causing a premature breakthrough at the production well. In this particular case of segregated forward combustion, the air stream moves parallel to the combustion front. Molecular diffusion and transverse mechanical dispersion will be insufficient to cause all the oxygen in the air stream to reach the combustion front. When the oxygen in the air stream is not completely consumed in the combustion process, it will reach the production well and create a serious fire hazard. In addition, the reduced efficiency may make the process economically unprofitable while also serious corrosion problems may be experienced in the production we11.3 This undesirable situation should, therefore, be prevented. However, in a situation as depicted in Fig. 1, an unstable temperature gradient exists in the gas phase. The combustion is taking place at the lower boundary at a nearly constant temperature that may be anywhere from 600 to 1,200F, depending on the conditions. The upper boundary of the gas phase is overlying, impermeable rock; its temperature might be around 100F, but may increase to 300F or higher due to conduction and convection as the combustion process continues. This represents a steep temperature gradient and it is conceivable that under those conditions free or natural convection will take place in the gas

Jan 1, 1967

By H. A. Bright, H. C. Vacher, J. G. Thompson

The methods employed for the determination of oxides and oxygen in ferrous materials may be roughly classed in two groups, "wet" methods and "hot" methods, the first group including the iodine, electrolytic, mercuric chloride, hydrochloric acid, nitric acid, and chlorine methods; the second group including the vacuum-fusion and hydrogen-reduction methods. The wet methods depend upon preferential solubility in a selected medium to separate the metallic portion of the sample from the oxygen-containing constituents. Subsequent analysis of the insoluble residue permits the isolation and separate determination of individual oxides and compounds. The hot methods depend upon the reduction of the oxide constituents of the sample by means of carbon or hydrogen at elevated temperatures. With the exception of the recently developed fractional vacuum-fusion method, the hot methods do not identify individual oxides and compounds but yield only a single value representing the sum of the oxygen contents of several or all of the oxide constituents present. With such diversity in the principles and aims of the different groups, it is not surprising that concordance of results by different methods has usually been difficult to obtain. The present cooperative attempt to define more rigorously than has been possible heretofore the accuracy and limits of usefulness of the various methods, originated in correspondence between Dr. John Johnston, Director of Research of the United States Steel Corporation, and other interested metallurgists. The plan was, briefly, to submit identical samples to a number of laboratories for analysis by different methods and to collate the results of these analyses. The project was endorsed by the Iron and Steel Division of the American Institute of Mining and Metallurgical Engineers at the annual meeting in February, 1933, and has been conducted under the joint sponsorship of the Iron and Steel Division and the National Bureau of Standards. The latter organization undertook

Jan 1, 1937

By C. M. Sellars, F. Maak

Electvomotie -force measurements hazle been made on ten Au-Ni alloys at temperatures 7754 825O, 900O, and 935°C using galvanic cells with solid electrolyte. Partial and ivtegral thermodynamic functions are derived from the determined activities. which show la9,ge positive deviations jvom Raoult's law. The enthalpies of mixing- are in close accord with calorinletric data and are of comparable accuracy. The results are used to determine the miscibility gap and the spinoidal curL1e, and are qlalitaticely interpreted in terms of the large size difference and electvonic interactions between gold and nickel. Tabulated nalues of the actielities and partial and inteqal free energies, entropies , and enthalpies of mixing are given in the appendix. The Au-Ni binary alloys are of particular interest thermodynamically as despite the large size difference between gold and nickel atoms they have a simple phase diagram.' This shows complete solid solubility above a miscibility gap with a maximum at about 71 at. pct Ni and 810°C. Activity measurements (over a range of temperature) have been made previously on this system using an electrolytic-cell method with a liquid chloride eletrolyte. The accuracy of this data has, however, been queried3'4 as it leads to values for the enthalpy of mixing which are too high when compared with calorimetric measurements.46 Also, the entropy of mixing is too high when compared with the values derived from specific-heat measrements. It was therefore considered worthwhile redetermining the activity data using a galvanic cell with a solid electrolyte (0.85 ZrO, 0.15 CaO). This method is based on a technique introduced by Kiukkola and aner'' and has been used to determine the thermodynamic data for Cu-Ni alloys.' THE ELECTROLYTIC CELL The cell used to determine the activity of nickel in Au-Ni alloys was: The cell reaction, which is discussed for a similar cell by Rapp and Maak, gives a direct measurement of the activity of nickel in the alloys as where aNi(alloy) is the activity of nickel in the alloy, 3 is Faraday's constant, E is the measured electromotive force, R is the gas constant, and T is absolute temperature. For the valid application of this type of cell the arrangement must be ther modynamic ally stable, which means that: 1) The free energies of formation of the oxides fulfill the relation 2) The vapor pressures or dissociation pressures of each component must be so small that during the time of the experiment the amount of any material transported by the gas is negligible. 3) Side reactions which change the alloy composition must be negligible. These reactions are possible both with the surrounding gas atmosphere and with neighboring solid material. The first two conditions are fulfilled by the above cell.' The third condition is approached by care in the experimental technique. The factors which control the attainment of equilibrium in this type of cell have been considered by Rapp and aak, who conclude that metallic diffusion in the alloy is the rate-control ling step. A lower temperature limit for the practical application of this cell is therefore set by the condition that equilibrium must be attained in reasonable times. EXPERIMENTAL MATERIALS AND TECHNIQUE The starting materials were mint gold (99.99 pct Au) and Mond nickel (99.9 pct Ni). Alloys, nominally 5 at. pct Ni and then each 10 at. pct across the system, were produced by vacuum-levitation melting compacts of mixed drillings of the pure metals. The nickel used for the reference tablets in the cells was melted in a similar manner. The alloy ingots, cast in boron nitride molds, were cold-forged and

Jan 1, 1967

By Charles S. Barrett

Metallurgists are making use of the stereographic projection to a steadily increasing extent. In the last five years no less than 20 papers in American metallurgical journals alone have employed the stereographic projection; recent books on physical metallurgy, plastic deformation, X-rays and their applications, and crystal structure use it. Mineralogists have used the stereographic projection for many years in the description of symmetry classes and crystal planes, for it presents an accurate, easily understood plot of any angular relations in crystals with all unessential features eliminated (such as the accidentally determined size and shape of crystal faces). In metallography and physical metallurgy the projection is much used for the analysis of markings appearing on polished grains: slip lines, twins, cracks, structures formed by precipitation, magnetic-powder patterns, etch pits, etc. Data from certain types of X-ray photograms are most conveniently analyzed by its use, particularly those for determining the orientation of single crystals or the preferred orientation of grains in an aggregate. Calculations of how to tilt or cut a crystal parallel to a certain crystallographic plane or to reflect X-rays from a certain plane are rapidly carried out. It has been adopted almost universally to the exclusion of other methods by those studying the deformation of metallic crystals, save where the accuracy required is greater than a few tenths of a degree. Any directional property in a crystal or polycrystalline material can be shown on a stereographic projection; for example, the modulus of elasticity, yield point, etc. It has been repeatedly called to our attention that there is need of an elementary explanation of the principles and methods of stereographic projection, covering all the common applications in the field of metallography and physical metallurgy. The following contribution is an attempt to fill this need. The description of each method is supplemented with references to publications in which the method has been used. For convenience to the reader, these illustrative references are chiefly in American journals, particularly the publications of the American Institute of Mining and

Jan 1, 1937

By W. F. Carew, F. A. Crossley

IT has been reported that the Ti-8 pct A1 alloy is ductile as water quenched from 800°C but brittle as annealed at 650 °C." The present, somewhat limited, investigation was undertaken to discover the cause of the embrittlement. In order to evaluate to some extent the continuity of the embrittling phenomenon, alloys of 6, 8, and 10 pct A1 were studied. Subsequent to the completion of most of this work, Ence and Margolin reported that a Ti,A1 phase exists and that two or more unidentified compounds may exist in the Ti-A1 system.' Materials, Equipment, and Techniques The alloys were prepared using Kroll process sponge of 124 Bhn hardness. In addition, some 8 pct A1 material was made with iodide titanium. The sponge-base alloys were prepared as melts of 4 lb or more by double arc melting. The iodide Ti-8 pct A1 alloy was prepared as 200-g buttons. The alloys were forged at temperatures of 980" to 1150°C. Results of chemical analyses are given in Table I. A Baldwin-Southwark 60,000-lb capacity tensile machine, equipped with an autographic stress-strain recorder, was used for the tensile tests. Standard tensile test specimens, 0.252 in. diam, were used. Standard Charwy V-notch impact specimens were tested using a -kiehle machine. specimens were sealed in evacuated Vycor bulbs for heat treatment. Powder samples for Debye-Sherrer anal- ysis were prepared by filing and screening through 325 mesh. The —325 mesh fraction was taken in an effort to concentrate a microstructural constituent assumed to be less ductile than the a phase. The powder samples were stress relieve2 by annealing

Jan 1, 1958

By Fred C. Bond

AN improved method of measuring the surface area of a comminution product down to any desired particle size has been developed. The method is largely graphical, and requires relatively little calculation. It can be used with materials containing large amounts of clay, or excess fines of any kind. The surface area S is expressed in terms of square meters per100 c.c. of solids. This expression is based upon volume rather than weight, and is considered to be more suitable for crushing and grinding problems, where the machines ordinarily are operated under constant volume conditions. It has the advantage that surface areas of different materials can be compared directly, even though their specific gravities may be unknown. The "specific surface" of a material, or the number of square centimeters of surface area per gram, is equal to 100S divided by the specific gravity. Particle diameters are expressed in microns, K being the diameter of the largest particle present and L the grind limit, or lower size limit of the particles formed directly by grinding. The value of K does not always coincide exactly with the diameters of the largest particles retained on the coarsest testing sieve, since the largest particles formed in crushing and grinding are often slabby, or have other irregular shapes. L has been chosen as 0.700 microns, or number 27.5 in the size number series,1 for reasons to be explained later. S is the total surface area of all particles larger than L microns in diameter. When a homogeneous comminution product is separated into fractions whose diameters bear a constant geometrical relationship [p] to each other, and the log per cent weight retained upon each size and passing the next larger size is plotted against the log diameter, a straight line results, which is called the distribution line, and which has a slope in called the distribution modulus. The distribution line can be extended to any desired limiting size, and the total surface area of all particles larger than that size can be calculated. The equation of the distribution line is w = Cxm [I] where w is the per cent weight retained on each successive sieve; x is the particle diameter; and C is the per cent weight retained on an opening of unit diameter.2 Theoretically, the distribution line can be extended to include infinitely small particles. When it is so extended, and the assumption is made that no fine particles are present other than those accounted for by the equation; the log per cent cumulative weight passing any series of sizes, plotted against the log diameter passed, will result in a straight line lying parallel to and above the plotted distribution line.

Jan 1, 1941

By C. M. Wayman, J. F. Breedis

The crystallography of the martensitic transformation in the Fe-30 Ni alloy was reinvestigated. The scatter in the habit Plane as determined from measurements on the mid-rib plane was smaller than reported previously, and the orientation relationship was determined from a martensite plate having known direction cosines. From agreement with crystallographic theory and from observations of the morphnlogy of the martensite plates, it is suggested that the mid-rib plane represents the starting region of the transformation. THE crystallography of the martensitic transformation in the iron-nickel system has been the subject of many investigations.&apos;-7 However, for iron alloys containing approximately 30 wt pct Ni, a wide scatter in the reported habit planes exists. In only one instance has a Laue determination of the orientation relationship been made, but the habit plane of the martensite plate studied was not determined experimentally. Because the most successful thermodynamic and kinetic analyses8 of the martensite transformation have been based on Fe-30 Ni alloys, it was considered desirable to reinvestigate the crystallographic features of the transformation in this alloy. Lieberman9 suggested that the most significant information for use in a theoretical treatment involves the determination of all the crystallographic observables from a single plate of the product phase. This was first done in essence by Greninger and Troiano10 for Fe-22 wt pct Ni-0.8 wt pct C, and is the method followed in this investigation. Some theoretical approaches11-13 in describing the martensitic transformation consider the overall transformation distortion to be comprised of a Bain distortion, or lattice deformation (PI, which produces the structure change, and a lattice invariant deformation (G), such as twinning, which together leave the interface or habit plane un-distorted. The incorporation of a rigid body rotation (R) results in a transformation distortion (E) such that the interface plane is left both undistorted and unrotated. In matrix notation, E = RPG where the lattice invariant deformation has "taken place" in the austenite. Bowles and Mackenzie14-16 in formulating a theoretical approach proposed an adjustable scaler quantity, denoted as 6, which represents a uniform dilation in the interface plane. This dilation acts to adjust the lattice spacings of the parent and product structures at the plane of contact. Using the dilation parameter as a variable, these authors were able to account for a continuous variation of habit planes in steels along a curve in the stereogram between {225}A and {259}A. she invariant line strain14 of the transformation is 6 RP, and the corresponding transformation distortion is E/6.) With the dilation parameter known, the invariant line is computed as the triple coincidence of the habit plane, the shear plane of the lattice invariant deformation, and the initial Bain cone.14 The contraction axis for the Bain distortion can be taken9&apos;17 as [010]A, and the correct permutation of the habit plane indices used. Kelly and Nutting 18 have established the shear plane (of twinning) in the tetragonal martensite of Fe-22 Ni-0.8C to be {112)M by means of transmission electron microscopy. The reasonable shear system is then {112}M which is equivalent to {011}A <01l>A. The as-

Jan 1, 1962

By W. C. Phalen

INTRODUCTION NOBODY will dispute the fact that the conservation in every legitimate manner of our valuable high-grade phosphate-rock deposits is a present-day problem of importance. The table and curve, given herewith, show. that during the past 10 years the exportation of high-grade rock has averaged very close to half the total output of the entire country. The bulk of this exportation is from Florida, for obvious reasons. It is plain that the deposits in this State, more particularly, are being wastefully depleted under a system of selecting the cream of the product for exportation to Europe, leaving the comparatively low-grade rock, running from 65 to 70 per cent., and under, in bone phosphate of lime, for our own n fertilizer manufacturers to work up when all the best rock is gone. In this paper the writer has endeavored to make a point of describing in some detail the important methods of production and conservation in Tennessee. These ought to prove of educational value to our American agriculturists and fertilizer manufacturers, and should result in a demand for the highest-grade rock, both for direct application to the soil and for use in making acid phosphate. It is certainly evident that the European

Jan 10, 1916

By P. E. Arnold, G. S. Ansell

RELAXATION in metals has been studied in detail by many workers in recent years.1-5 These studies have shown that there is an energy-loss peak observed in a metal placed in mechanical resonance at low frequencies which may be correlated with various metallurgical processes. These experiments have been largely used to study single-phase materials. In order to study the effect of a finely dispersed second phase in a metal matrix upon this phenomenon, the relaxation behavior of an aluminum-aluminum oxide SAP-Type alloy in both the fine-grained as-extruded and coarse-grained recrystallized conditions was investigated by the use of internal-friction measurements. The alloys studied, designated MD 2100, consist of a matrix of commercial-purity aluminum containing a finely dispersed second phase of aluminum oxide. The aluminum oxide is present in this alloy in the form of fine platelets approximately 130A units thick and several microns on edge. The mean free path betwen dispersed platelets is approximately 0.5 p. The grain size of this alloy is extremely stable at temperatures as high as the melting temperature of the aluminum matrix. In the as-extruded condition the grain diameter is several microns, while in the recrystallized condition it is several millimeters in diameter. The damping characteristics of the alloy samples were determined using a torsional-pendulum device. The internal-friction constant was determined for this alloy in both the fine-grained as-extruded and coarse-grained recrystallized conditions over the temperature range from 343" to 923°K at frequencies of 0.9, 1.3, and 1.8 cycles per sec. An internal-friction peak was observed in testing the fine-grained alloys which was not observed for the coarse-grained alloys. This peak, which might be associated with a type of grain-boundary relaxation, was observed at each of the three different test frequencies for the fine-grained sample. The temperature at which the relaxation peak occurred for each of the three different frequencies is shown in Table I. From these data an activation energy of relaxation for each pair of frequencies was determined by comparing the temperature shift of the relaxation peak with frequency between each of the test frequencies, assuming that an Arrhenius-type rate equation is applicable. The activation energy of relaxation determined from these data is also shown in Table I. The mean value of the activation energy was about 6 kcal per mole. The activation energy for the relaxation process determined in this investigation indicates that the relaxation associated with the grain boundaries in this aluminum-aluminum oxide SAP-Type alloy is quite a different process than grain boundary relaxation in single-phase aluminum alloys. In these latter alloys, the activation energy for relaxation has been found to be the activation energy for self-diffusion, approximately 36 kcal per mole1,2 Where the activation energy is the same as the activation energy for self diffusion, it has been proposed that the relaxation phenomena is dependent upon vacancy formation and motion. It is apparent therefore, that, in this aluminum-aluminum oxide SAP-Type alloy, the relaxation must be due to another type of atom transport. It has been shown previously in studies of the high-temperature, low-stress, steady-state creep behavior of as-extruded aluminum SAP-Type alloys, that the activation energy for steady-state creep is one that may be characterized by the nucleation of dislocations from the grain boundaries. It is proposed that the relaxation behavior observed here is due to a similar effect. In this case, the internal-friction peak is a resonance behavior due to the time-dependent nucleation of dislocations from grain boundaries in the sample. A process of this type would have an activation energy which is undoubtedly stress-dependent and of the form Q = Q, + (dQ/du)u

Jan 1, 1962

By Herbert H. Kellogg, Nathaniel Arbiter, Arthur F. Taggart

THE experimental work herein described is presented in support of the following broad hypothesis: Conditioning of metals and metallic sulphides by amine collectors involves metathetic reaction at the solid surface between the collector and an oxidized metallic compound, to produce a coating comprising an amine-bearing compound of low solubility in the system. The type of reaction is different in acid and in basic solutions; both types may occur simultaneously in near-neutral pulps. EXPERIMENTAL The experiments comprise contact-angle tests with a variety of metals and metallic sulphides and extraction tests on ground chalcocite. Contact-angle tests were made principally on metals. Covellite paralleled metallic copper in amine solution at pH 8.8 (Table 3) and in alkaline water, but maintained an angle of about 70° in 10-3 HCl solution, where metallic copper lost its angle. The tests with anionic collectors (Table I) indicate that the behavior of metals in general is parallel to that of their minerals in anionic solutions. It is believed that this is generally true with cationic collectors also, but the covellite test is a warning against a broad assumption to this effect. All test specimens were mounted in Transoptic.* All tests in conditioning solution were preceded by a test in distilled water; cleaning and polishing were continued in every case until the angle in water was zero. Subsequent transfers into and out of solutions and test cells were made in such a way as to prevent exposure of the surface to air.1 The amine used was primary laurylamine, Armour and Co., AM-1120. It was used in the form of the hydrochloride, obtained by precipitation with gaseous hydrochloric acid from an ether solution of the amine, and purified by two recrystallizations from ether-alcohol.2 Inorganic and other test reagents were standard laboratory grades. [ ] Temperatures were not controlled; the probable range of test-solution temperatures is 65° t0 80°F.

Jan 1, 1943

By H. I. Aaronson

ONLY limited studies have been made of pro-eutectoid a morphology in hypoeutectoid Ti-Cr alloys during previous investigations, 1-3 The nature of the eutectoid reaction, ß?a + TiCr2, has been considered in somewhat more detail.1,2,4,4 Inasmuch as the proeutectoid ferrite reaction in plain carbon steels has recently been extensively investigated in this laboratory, advantage has been taken of the opportunity to compare the morphologies developed in two rather different eutectoid systems in order to permit a preliminary estimate to be made of the degree of generality which may be ascribed to the various results obtained. Experimental Procedure The chemical analyses of the alloys used are given in Table I. The 7.22 pct Cr alloy was prepared by the Battelle Memorial Institute from iodide titanium and high purity chromium. The initial ingot was made by arc melting a master alloy and iodide titanium. The resultant ingot was twice remelted. by the consumable electrode technique. Upset forging at 950°C reduced the final ingot to 3/4 in. sq bars. The 10.94 pct Cr alloy was prepared by the Titanium Metals Corp. of America from sponge titanium and chromium of ordinary purity. This alloy was melted twice by the consumable electrode technique, forged at 1200° to a 3/4 in. sq bar, and rolled at 815°C to a 1/2 in. round. Specimens 1/4 in. x 1/4 in. x 1/16 in. were cut from the 7.22 pct Cr alloy; halves of disks 1/2 in. in dlam and 1/16 in. thick served as specimens of the 10.94 pct Cr alloy. These specimens were individually encapsulated in Vycor, Each capsule was evacuated three times to a pressure of 2 to 6 x lo-&apos; mm Hg and flushed twice with a reduced pressure of argon prior to sealing. The inclusion of two small packets of zirconium chips permitted the capsules to be outgassed and internally gettered, without heating the specimen, prior to heat treatment. The specimens were solution annealed for 40 min at 1000°C, isothermally reacted in deoxidized lead pots, and quenched in iced water. Most of the isothermal reaction treatments were carried out at 25" intervals between 725° and 550°C on specimens of the 7.22 pct Cr alloy and at 650°C on specimens of the 10.94 pct Cr alloy. Results and Discussion Morphologies of Proeutectoid a*—Kinetics of the ß?a Reaction: Fig. 1 shows the TTT-curves for the beginning of the proeutectoid a and the eutectoid reactions in the temperature range investigated in the 7.22 pct Cr alloy. The M, temperature in this alloy is below 0°C. The curve for the beginning of the proeutectoid a reaction is in good agreement with that of Frost, Parris, Hirsch, Doig, and Schwartz&apos; for a 7.54 pct Cr alloy, appears at considerably earlier reaction times than the corresponding curve presented by Rostoker4 for a 7 pct Cr alloy, and lies athwart the curve of Spachner and co-workers11 for an 8 pct Cr alloy. Differences in criteria for the beginning of the a reaction and the relatively high rate of this reaction at lower temperatures presumably account for some of these divergences and may also explain, in part, the apparent failure of an iodide-base 7.22 pct Cr alloy to react more slowly than sponge-base 7 to 8 pct Cr alloys. Grain Boundary Allotriomorphs: Crystals of this morphology nucleate at and grow preferentially and more or less smoothly along the matrix grain boundaries.5-7 Allotriomorphs are the first morphology to precipitate at most grain boundaries at reaction temperatures from 725°C, the highest temperature studied, at least through 575°C. Fig. 2 Shows typical allotriomorphs, formed during an early stage of transformation at 725°C. Grain boundary allotriomorphs are not the predc=iaant morphology at late reaction times at any temperature studied. However; from 725" through

Jan 1, 1958