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By H. M. Stewart, R. A. Grange

Man.; steel parts may crack if quenched directly into a bath near room temperature, but not if quenched at a temperature just above the range where martensite forms and then allowed to cool slowly to room temperature. This latter procedure, which is the basis for such modern hardening techniques as "martempering" and "isothermal quenching," may entail some sacrifice in depth of hardening but very little, if any, in intensity of hardening. In planning such treatments, it is necessary to know the upper limit of the martensite range, and often desirable to know the proportion of martensite that would form on cooling to any lower temperature; furthermore, the tendency of a particular steel to crack when quenched is unquestionably associated with the temperature range of martensite formation, and consequently knowledge of this range aids in selecting the optimum composition for a given application. Certain puzzling phenomena associated with the properties of quenched and tempered steel may be at least partly clarified as the manner in which martensite forms is more fully understood. Information on the temperature range of martensite formation, particularly with respect to how much martensite results from quenching to a given temperature, is lacking for most commercial types of carbon and low-alloy steel. These considerations led us to study martensite formation in 14 carbon and low-alloy steels. The resultant data may be directly used in the following ways: (I) for selecting the lowest quenching temperature at which no martensite will form; (2) for selecting the highest quenching temperature at which virtually all marten . site will form, thereby avoiding quenching to an unnecessarily lower temperature with attendant danger of cracking; and (3) in producing a mixture of tempered martensite and bainite, which in high-carbon steels has been found to possess somewhat better ductility than tempered martensite, yet does not require the full transformation time necessary for a completely bainitic (austempered) structure. PART I. OBSERVATIONS OF MARTENSITE FORMATION IN FOURTEEN CARBON AND LOW-ALLOY STEELS Transformation of austenite to pearlite or bainite can be conveniently studied by observing the change that occurs over a period of time at constant temperature; such studies are the basis of the isothermal transformation diagram (S-curve). This isothermal technique is not applicable to martensite formation, which occurs within a time interval too small to measure, at least by any ordinary means. For all practical purposes, therefore, martensite may be regarded as forming only during cooling and not during a period of time at constant temperature. As austenite is cooled below

Jan 1, 1947

By AIME AIME

AN outstanding session of the Annual February Meeting was one held under the joint auspices of several groups on Tuesday afternoon, Feb. 22, as a symposium on the question of preserving peace in the postwar era through the control of the supply of sundry minerals vital to the Axis nations. D. H. McLaughlin and R. C. Allen were associate chairmen. And C.K. Leith led the discussion.

Jan 1, 1944

By F. E. Bash

Constantan is an alloy of copper and nickel that is extensively used, under a number of trade names, as a resistance wire with a low temperature coefficient of resistance, and one of the elements of base-metal thermocouples, iron usually being the other thermoelement, although for low-temperature work copper is also used. Before the war, constantan was imported, in common with many other technical necessities. Since it required considerable time to receive the constantan after it was ordered, fairly large stocks were kept on hand; but after the beginning of the war no more was imported and the stocks of foreign material were exhausted about the same time that the steel and munition manufacturers began to need great quantities of it for thermocouples for the heat treatment of steel. To meet this demand, the International Nickel Co. began manufacturing constantan that met all the requirements of the users of resistance wire but did not give the same electromotive force against iron as the German material and consequently could not be used with instruments calibrated for a definite e.m.f.-temperature relation. It so happened that all the constantan made had an e.m.f. lower than that necessary to meet the specifications of the Leeds & Northrup Co. for whom this investigation was carried out. If some had been higher and some lower, good wire could have been obtained by a process of selection, but as it was no wire at all could be procured. To remedy this situation, a thorough investigation was started with the close cooperation of the International Nickel Co. and the Electrical Alloys Co. The specifications to which the constantan had to conform were that it should give an e.m.f. of 47.40 millivolts against pure iron at 1500" F. (816" C.) with the cold-junction temperature at 0" F., or a proportional e.m.f. at temperatures near 1500" F. The method of checking a wire was as follows: It was first welded to a piece of iron wire; Armco iron was found to be satisfactory but iron with greater than 0.1 per cent. carbon would give a lower e.m.f. against the same piece of constantan than pure iron. The couple was then insulated and the fire end was tied to the

Jan 1, 1921

By H. H. Rachford, and J. D. Rice

The effectiveness of digital computing machines in making technical calculations depends on how well the work is arranged to utilize the capability of the machines. This note presents a particularly useful way of calculating hydrocarbon vapor-li.quid equilibrium in the flash vaporization (or condensation) system. The method is well suited to sequence-controlled computing equipment. It is not limited to equilibrium calculations and may be used for solution of most implicit equations in one variable. INTRODUCTION There is increasing interest in the use of electronic digital computers in research and engineering calculations. This is a fortunate and inevitable trend in view of both the increasingly extensive numerical work which is becoming a routine part of many daily production operations and growing demand for the overwhelming amounts of calculations required by newly developed numerical methods for solving heretofore unsolved problems. Machines are in many ways ideally suited to the task but of necessity present certain difficulties. for a particular poblem to be solved must often be formulated quite differently from the way it would be arranged for manual solution. This is done in order to take advantage of the inherent speed and precision of electronic computers and at the same time to limit the need for number storage to the capacity of the machine. Therefore, this note is submitted to present a general and quite powerful method of finding solutions of the frequently encountered implicit equation: F(x,y1,y2,...ya)=0.......(1) where the root, x, is to be found for a given set of y1, ... yn.. The procedure is well suited for use with computing machines, for it usually requires but little storage or programming beyond that necessary to evaluate F. HYDROCARBON EQUILIBRIUM The method is described in terms of the problem it was designed to solve, i.e., the calculation of hydrocarbon vapor-liquid equilibrium in flash vaporization. Given the composition of a hydrocarbon mixture and appropriate values of the equilibrium ratios K, to find the phase ratio and compositions in a closed system: let z, be the mol fraction of the i-th component in the mixture. If K, is the ratio yl/xl, where y, and x,

Jan 1, 1952

By Cyril Wells, Robert F. Mehl

THE practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out 1,13 This importance ties chiefly, though by no means only, in the study of carburizing and in the study of reactions involved in the eutectoid inversion in steel The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in y-Fe and their mutual effects are measured with precision The present paper reports the results of meas¬urements of diffusion coefficients D of manganese in -y-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients [$] Data on the rate of diffusion of manganese in y-Fe have been reported by Fry2 and by Paschke and Hauttmann 3 Claussen4 calculated the diffusion coefficient D from Fry's data as 3 X 10-10 sq cm per sec at 960°, which will be shown to be incorrect by many orders of magnitude Paschke and Hauttmann gave a rough value of 9 6 X 10-8 sq cm per sec at 1400° Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon METHOD AND MATERIALS Method -The method employed is identical with that used earlier 5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded The diffusion anneals were performed in argon, except one (test 18) in which hydrogen was employed for purposes noted below The temperatures reported are accurate to about 3° and constant within I°C , the diffusion times are reported to the nearest half hour The specimens were furnace-cooled after the diffusion anneal at about 2° per min Layers, usually 0 004 in thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0 01 per cent Mn, the distances of these layers from the interface was measured to ±0 0002 in The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions e The D values calculated by these two methods do not differ appreciably 5 The Grube solution was used except in tests in which the effect of concentration upon D was greater than 50 per cent, in such cases the Matano method, which explicitly provides for the variation of D with concentration,1 is the more reliable In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer In 3 of the 30 tests, however, this is not justified, and the D values

Jan 1, 1941

By R. Hoffmann

The Waelz process produces oxides of volatilizable metals from ores, metalliferous products and residues. The process was originally used for recovering zinc and lead, where tailings and residues containing those metals had accumulated at mines or smelters, but it is applicable for obtaining tin, arsenic or other volatilizable metals. It is useful when other methods of obtaining the metals from the ores or residues are too difficult or expensive or show too low a recovery. The Waelz process was developed in 1923 for the treatment of large calamine dumps in Upper Silesia, which showed zinc contents of 8 to 10 per cent. and lead contents up to 3 per cent. The rapid development of the process, from the first trials up to the plants now working or in course of erection, is shown in Fig. 1. The first industrial Waelz plant was started in 1925. Within two years the capacity of the working plants reached 700 tons material per day of 24 hr. During the year 1928 the daily capacity of the plants now at work or in course of erection will rise

Jan 1, 1928

By J. D. Embury, R. M. Fisher, A. S. Keh

An investigation of the defect structure and properties following large strain deformation has been carried out using transmission electron microscopy and mechanical testing for a range of ferrous materials and for copper. It is shown that, for a variety of ferrous materials, a cellular substructure is developed during the initial stages of working and on further deformation the dimensions of this substructure are reduced. Quantitative measurements of the flow stress and the scale of the substructure indicate that the strength of heavily worked materials is largely determined by the spacing of cell walls. These cell walls act as dislocation barriers in a manner analogous to grain boundaries. FCC materials do not harden as extensively as bcc after cold working and the present observations on copper indicate that the dimensions of the substructure in fcc materials are not markedly reduced on deformation. The differences between the fcc and bcc structures produced by large plastic strains are ascribed to differences in the extent of dynamic recovery. It is tentatively proposed that the greater stability of substructural barriers in bcc structures results from strong interstitial Pinning effects. It is proposed that for large plastic strains the work-hardening process may be considered in terms of the reduction of substructural-barrier spacing during the working process. This pvovides a simplified hut useful analysis of the strain hardening occurring during mechanical processes. THE mechanisms of strain-hardening processes have occupied the attention of numerous investigators over the past three decades and a multitude of theories have emerged in this field. The majority of previous work has been concerned with the development of a description of the plastic behavior of single crystals in terms of dislocation theory.'" In contrast, scant attention has been given to the strengthening mechanisms operative during mechanical working processes such as rolling and drawing. The large plastic strains involved in these processes make it difficult to correlate the observations with any elementary dislocation theory. Further, as Bullen and coworkers3 have opined, for large plastic strains both hardening and recovery occur simultaneously and thus it is extremely difficult to estimate the effect of plastic strain on the ambient internal stress field. It is probable that for large plas- tic strains any theoretical estimate of the internal stress field must be made in terms of complex dislocation groups. Although some valuable theoretical work has been done toward calculating the elastic properties of dislocation groups4 any detailed self-consistent model for large plastic strain is as yet impossible. With these limitations in view it is still of value to examine the mechanical properties of highly strained materials as a function of their substructure. This relationship is explored in the present communication for a variety of materials subjected to rolling, drawing, or swaging. The primary object of this investigation has been to establish the validity and the limitations of the substructural strengthening mechanism proposed by Embury and eisher' for drawn pearlitic wire and by Meieran and Thomas for drawn tungsten wire. No attempt has been made to delineate the basic interaction mechanism which occurs between a slip dislocation and the substructure and the authors believe that a great deal more experimental evidence must be compiled before these fundamental aspects can be explored. Also, no specific attention has been given to the detailed formation of substructure during working. Experimental Details. A variety of materials were used in this investigation, the compositions and heat treatment of which are tabulated in Table I. The commercially pure iron is referred to throughout this report as Ferrovac E. The mechanical working processes were all performed at room temperature. The wire drawing was performed on a manual drawing bench. Reductions of between 10 and 20 pct in area per pass were used in both swaging and drawing. The experimental parameter used to evaluate the mechanical properties of the materials was the 0.2 pct proof stress. This was determined for wire samples using an Instron tensile machine at a crosshead speed of 0.02 in. per min. The techniques for preparation of samples for transmission electron microscopy have been described previo~sl~.~ Specimens from wire samples were prepared from longitudinal sections and in some cases from transverse sections. To evaluate the substructural characteristics of rolled materials, thin foil samples were prepared of both the face and edge sections. Results. One of the more familiar ways of expressing work hardening in mechanical working is by the flow stress as a function of reduction in cross-sectional area. Fig. 1 shows such a plot for Ferrovac E eutectoid carbon steel and for copper. The curve for Ferrovac E is characterized by an initial stage of rapid work hardening and a final stage of rapid work hardening separated by an intermediate stage with a low rate of work hardening. This behavior is typical of many ferrous materials and the drawn pearlite wire previously investigated by Embury and Fisher is a more pronounced example. Copper shows an initial

Jan 1, 1967

By Robert Wamsley, W. E. Jones

ONE of the earliest problems in the life of any community is the provision of an adequate supply of water sufficiently free from all types of contamination to be suitable for domestic purposes. Generally speaking, the location of most communities is determined to a great extent by the availability of an adequate supply of satisfactory water. For a mining camp, that consideration cannot be foremost. Here, the ore takes first place, and the men who mine it must do the best they can under the existing conditions. If there is no local source of water, it must be brought from some distant source or must be found by sinking shafts or drilling wells. Fortunate indeed is the mining company that discovers a commercially valuable ore deposit beside a never failing creek full of pure water, with sufficient water rights available, because the acquisition of water in any other manner nearly always involves not only a considerable period of time but the expenditure of considerable money. The experience of Climax Molybdenum Co. demonstrates the measures that sometimes are necessary in order to provide a suitable supply of water. The Climax mine and mill are on the Continental Divide, about 13 miles northeast of Leadville. The elevation of the domestic part of the camp varies from a minimum of 11,320 ft. to a maximum of approximately 11,550 ft. above sea level, and, as is common at such altitudes, the near-by streams that might be suitable for a water supply are small and intermittent, usually flowing only during the summer months. The only streams of any size in the immediate vicinity of Climax are the Ten Mile and Arkansas Rivers. The headwaters of Ten Mile River are on the Company's property, and its water has been used for the domestic supply. The headwaters of the Arkansas River are about 2 miles distant and have not been used as a source of supply by the company. During the past 11 years of the production of molybdenum at-Climax, the number of families living there has increased from about 45 to 283, and the population has increased from about 200 to 1200 persons. Consequently, the capacity of the water-treatment facilities, and the amount of water available, had to be increased to meet the requirements of the camp. As early as 1932 it was recognized that the water in Ten Mile River would not continue to be adequate for domestic purposes and after considerable discussion it was decided to drive a drift through the major fault in an effort to find additional water. This drift was completed in 1935 and tapped sufficient water to make the supply adequate. This water was treated in a tank underground, where lime was added, and was then piped into the domestic supply lines. At about the time this line was completed, the presence of fluorine in harmful concentrations was discovered in the water. This problem was submitted to the International Filter Co. and in November 1937 a plant of its design was put in operation for treating the water to remove the fluorine. This plant proved entirely successful,

Jan 1, 1945

By J. J. Kanter

A. I. Blank.*-—Mr. Kanter has spoken of failures from causes other than creep itself in metals that are subjected to creep stresses. Would it be possible for the author to enlarge on this very important matter of "cataclysmic types of failures? " J. J. Kanter.—Of course, it is always a delicate matter to discuss specific failures. I would prefer to keep the present discussion on fundamentals and principles. H. L. Burghof.*—Mr. Kanter, I should like to ask what you consider the responsibility of the designer in avoiding stress concentrations that would lead to these types of failures? J. J. Kanter.—lt was my feeling in looking over the papers of this symposium that they were significantly lacking in consideration of what happens to the metals when strained under conditions that lead to rupture. Often creep tests are run that produce only a fractional percentage of the deformation, in several thousand hours. That kind of information gives the designer no assurance whatever that cracks will not result in his structure at points where stress concentrations, and therefore deformation concentrations, exist. I think anyone in this day and age who presents a paper on creep should incorporate with those studies a thorough investigation of creep rupture if it is expected to make an impression upon the design engineer.

Jan 1, 1945

By David J. Reddish, Barry N. Whittaker

The characteristics of surface ground strains due to longwall mining are reviewed with special reference to U.K. coal mining observations. The current empirical method of estimating ground strain is discussed. A method of determining surface ground strain above a longwall extraction is described whereby strain can be accurately represented along a line in any direction. The discussion is supported with examples of its application to common subsidence engineering problems.

Jan 1, 1984

By B. C. Allen

The solubility of chromium in liquid silver and that of molybdenum and tungsten in liquid tin have been determined by equilibrating Ike Liquid in a crucible of the solule metal. Generally the weight of solute in solulion was delermined both chemically and from crucible weight losses. The resulting weight percent solubilily of chromium in silver as a function of absolule temperature T is given by log w = -6660/T + 4.02 in the range 960° to 1445°C, and that of molybdenlttrl in tin by log w = —5050/T + 1. 79 in the range 1200° to 2200°C. The values appear unaffected by minor changes in solute composition. Calculations aye made of the parlial molar heal and excess entropy of mixing. The estimated solubility of tungsten in tin is 0.001 pct at 2000°C. Evidence is presented that molybdenwm dissolves in tin without compound for mation and that tungsten and tin form W10Sn. RECENT developments in coatings, heat transfer, and brazing require a knowledge of equilibrium solubilities in a variety of systems at elevated temperatures. Of particular interest are solid-liquid interactions in metal systems involving dilute solutions. This investigation was undertaken since little is known about the phase relations or solubility of chromium in liquid silver or of molybdenum and tungsten in liquid tin.1,2 EXPERIMENTAL WORK As indicated in Table I, high-purity metals or those of known impurity levels were used. Crucibles were machined from chromium, molybdenum, and tungsten bar stock 1.3 cm diam and 2.2 cm long. Chromium rod was prepared by arc melting and extruding iodide process crystals.3 The five chromium impurity alloys were in the form of 0.6-cm-diam swaged rod. A Cr-0.06N* alloy was prepared by exposure to NH3 at 1150°C in a closed quartz capsule for 24 hr. Because significant nitrogen was lost during annealing in argon at 1600°C,4 the estimated level was 0.01 pct N. Chromium and Mo,W crucibles were outgassed at 1200" and 1600°C, respectively, at 3 X 10-5 mm. The solvent was placed In crucibles of the solute metal- 6 g Ag in chromium, 0.4 g Ag in the five chromium impurity alloys, and 4 g Sn in Mo,W crucibles. The silver and tin series were outgassed at 900" and 110O°C, respectively, and held at the desired solution temperature in a tantalum resistance furnace under 1.05 atm 99.995 pct Ar. An equilibration time of 0.5 to 1 hr was chosen since 0.3-, I-, and 4-hr anneals at 1235°C for Cr-Ag yielded similar results. Temperatures were measured optically to +10°C under essentially black body conditions which were checked against the melting point of silver. The Cr-Ag and Mo-Sn,W-Sn series were respectively equilibrated at 990° to 1400°C and 1200" to 2000°C. Vaporization losses were generally held to <1 pct by the argon. In the 1800" and 2000°C anneals for 0.5 hr, the crucibles were placed in tightly sealed tantalum cans which kept tin losses to <5 pct. After the anneals, the specimens were furnace-cooled. One anneal was made on small Mo-0.02 C, Mo-0.5Ti-0.lZr, and tungsten crucibles containing tin at 2200°C. The metals were sealed in an electron-beam-welded tantalum can of minimum volume. After the anneal, tin was still present in each crucible, none of which was severely attacked. After equilibration, the saturated solvent metal was selectively removed from the crucible by acid leaching. Weight losses sustained by the crucibles were determined from the initial weight minus the final blank-corrected weight after acid leaching. Chemical analyses were performed on some of the samples. Hot 1:l HNO3-H2O removed silver from chromium with the blank running <0.1 mg or <0.002 pct on measured solubility. Tin was removed from molybdenum and tungsten by hot concentrated HC1 with the respective blanks amounting to -0.004 and -0.0004 pct in the presence of tin. The insoluble residues were weighed and checked for composition. The leaching solutions contained traces of the solute metals which were analyzed by colorimetric methods, Diphenyl Carbazide for chromium, Thiocyanate for molybdenum, and Dithiol for tungsten. The total of the two percentages found from the residue and leaching solution minus the blank gave the desired solubility values. On the basis of annealing empty molybdenum and tungsten crucibles, weight losses due to MoO3 or WO3 volatilization were found to be generally 10.4 mg and affect measured solubilities by <0.01pct. RESULTS AND DISCUSSION Chromium-Silver . Since no intermediate compounds are reported to form in the Cr-An system,&apos; crucible weight losses and chemical analysis of the entire melt should provide reliable measures of the chromium in solution. Values obtained by the two methods are in agreement as shown by the results for unalloyed chromium in Table II and plotted in Fig. 1. Furthermore, the results are consistent with those previously determined by melting equilibrated silver out of the crucible and analyzing calorimetrically for chromium.&apos; On the basis of limited thermal analysis data, the solubility of chromium in silver has been quoted as 8 pct at the monotectic temperature of -1445°C.1 This investigation indicates an extrapolated solubility of 1.38 pct which is believed to be more reliable. At the eu-

Jan 1, 1968

By R. A. Oriani

The partial molal volume of hydrogen is one of the parameters that describe the elastic interaction between the solute and the stress fields about inclusions, dislocations, and cracks. As such the partial molal volume is probably of importance in the elucidation of phenomena such as hydrogen embrittlement and hydrogen yield point. A knowledge of this quantity would also be helpful in thinking about the state of dissolved hydrogen in iron. However, because of the very low lattice solubility of hydrogen in iron the usual ways of determining the lattice expansion are not practicable. It is therefore of interest to apply the thermodynamics of stressed bodies to two sets of measurements of the effect of elastic stress upon the permeability of hydrogen in order to deduce a value of the partial molal volume, VH, of hydrogen dissolved in a iron. Beck ..&apos; and previously de Kazinczy, observed that a uniaxial tensile stress increases the permeability of hydrogen in iron and in various steels. Beck et 01. employed Armco iron and A.I.S.I. 4340 steel, whereas de Kazinczy used a steel the composition of which was 0.13 C, 0.23 Si, 0.46 Mn, 0.006 P, and 0.038 S. Upon releasing the stress the permeability increment disappeared if the stress was below the elastic limit. Both investigators employed cathodic charging to introduce the hydrogen. de Kazinczy measured the permeation through a thin-walled tube by collecting the gas, whereas Beck et al. measured the permeation through sheets of various thicknesses by a very sensitive electrochemical technique. Both investigators measured the steady-state permeation at constant rate of hydrogen ion discharge, and Beck measured in addition the hydrogen diffusivity by a time-lag technique which is independent of the boundary conditions. Beck et al. and de Kazinczy found a linear relationship between log (J,/Jo) and the stress, where Ju/Jo is the ratio of the flux of hydrogen when the metal is under uniaxial tensile stress, a, to the flux under zero stress, for the same temperature and charging current. Beck et al. found in addition that the diffusivity of hydrogen is not changed by stress. Both investigators concluded that the observed change in permeability is due to an increase in hydrogen concentration, and furthermore that the increase in concentration is due directly to the thermodynamic effect of stress upon concentration. Accepting this assessment of the situation for reasons given below, one may use the equation3j4 in order to evaluate I/H, the partial molal volume of hydrogen. This equation is valid for the domain of a/E «¦ 1 (where E is the Young&apos;s modulus) and under the assumption that hydrogen expands the lattice isotrop-ically. From the data of Beck el al, one calculates V7H - 2.0 cu cm per g-atom, and from those of de Kazinczy one obtains 1.8 cu cm per g-atom. That the increase of concentration with stress is indeed of thermodynamic origin is attested to by the facts that the experimental results conform to the thermodynamic relation, Eq. [I], and that the results are the same whether a pure iron1 or each of two different steels172 is used. Neither of these facts wou1.d necessarily be expected if the effect of stress were, rather, to increase the ratio kn/k, of the kinetic factors of the following competing reactions: H(ads) — H (dissolved) Such a change of kinetics at the surface could be an alternative explanation of the effect of stress on the permeability. Although this writer does not deem this explanation to be the correct one for the reasons given above, it must be admitted that unambiguous proof that the phenomenon has a thermodynamic origin does not yet exist. Two kinds of experiments may be suggested. One is to plate a variety of metals on the input surface of the steel and repeat the stress experiment at a variety of hydrogen charging currents. The other is to employ somewhat thicker specimens in order to be able to apply uniaxial compressive stress. Eq. [I] shows that ln(c,/c,) depends on the sign of the stress, but it is difficult to see a physical basis for which k2/kl would depend on the sign of a. The present value of V^ in a iron agrees with phragmen&apos;s5 estimate, which he based on comparisons with the lattice expansion by hydrogen of titanium, zir-

Jan 1, 1967

By J. D. Meakin, H. G. F. Wilsdorf

Using a combined decoration and etching technique the dislocation structure of annealed and deformed a brass has been studied. Annealed crystals revealed a low density forest and well-developed subboundaries; lightly deformed crystals contained discrete groups of dislocations. The dislocation density and the number of dislocations in a group were obtained from the micrographs. Using slip-line data, the mean path of a dislocation and the configuration of groups along an active slip plane have been deduced. Observations on secondary and cross-slip are reported. It has been the aim of many investigations to obtain detailed knowledge of the dislocation patterns which are present in metals before and after their deformation. The "decoration" of dislocations with impurity atoms has been considered as one of the promising experimental approaches, and much work has been done to develop this technique for revealing dislocation sites in metals. Following the early work by Castaing,&apos; Castaing and Guinier,&apos; and Lacombe and Berghezan~ on aluminum-rich aluminum-copper alloys, dislocations in this material have been studied extensively by others.+&apos; In these alloys the dislocation sites act as nuclei for the precipitation of the second phase. The main results of the investigations on aluminum with copper are: i) the confirmation of the earlier contention that subboundaries consist of dislocation walls, ii) that many more dislocations are found in slip bands than in regions where less glide had taken place, iii) the observation of individual dislocations, lying nearly parallel to the surface investigated, and iv) that parts of dislocation loops, apparently emitted from a dislocation source, could be made visible. Recently, Jacquet, Weill, and Calvert have succeeded in revealing nearly concentric dislocation loops in quenched A1-4 pct Cu and thus indicated directly the existence of dislocation sources in a fcc metal specimen of normal dimensions. Another decoration method developed by Dash10&apos;11 and applied to silicon crystals makes use of diffusing copper to the dislocations from a surface deposition. The dislocation pattern can then be observed by an infrared technique. His results include evidence for symmetrical and spiral Frank-Read sources, and for arrays of dislocation loops which follow simple crys-tallographic directions. Recently Low and Guard" have studied the dislocation structure of silicon-iron using carbon for the

Jan 1, 1961

By F. O. Shuck, F. E. Butler

A diaphragm diffusion cell suitable for use with liquid metals was designed and tested by measuring the diffusion coefficients for a Hg-10 pct In alloy at 25°C. The binary diffusion coefficient and the coefficients for In and Hg tracers were measured at this composition. The measured coefficients for both tracers were less than the binary diffusion coefficient. When these coefficients were combined with the activity correction term of Darken, the predicted binary coefficient was somewhat higher than the experimental value. In recent years a number of investigators have been studying diffusion of liquid metals in order to gain a better understanding of the liquid state and to examine possible applications to liquid metal processing. The bulk of this work has involved either self-diffusion or diffusion of low concentrations of solute metals in an essentially pure solvent metal. The most common experimental technique employed has been the capillary-reservoir method of Anderson and saddington1 since it is well-suited to measurements involving low concentrations of solutes. As an expansion of previous studies, an investigation of the variation of diffusion coefficient over large composition ranges has been undertaken in this laboratory. Although it is possible to modify the capillary-reservoir method for such measurements, the technique loses its principal advantage of requiring only small quantities of solutes. Therefore, it was felt desirable to investigate other possible experimental techniques applicable to measurements over large composition ranges. A technique which has been used widely in measurements of other liquid systems and seemed potentially applicable to studies of liquid metals was the diaphragm cell. This method has been found to combine relative simplicity of operation with accurate and reproducible results. In use with normal liquids, the tyiical diaphragm cell utilizes a porous glass disk. However, because of the high surface tension, it is not possible to use a diaphragm of such fine pore structure with liquid metals. Furthermore. projected use at high temperatures makes the use of glass undesirable. Consequently, the first problem was the search for an appropriate cell design. EXPERLMENTAL Diaphragm Cell. A number of possible cell designs were examined. Prototypes of several were constructed and tested. The final design is shown in an exploded view in Fig. 1. The cell consists of two identical chambers, one on either side of a 0.20-in.-thick partition. The chambers are 0.15 in. deep and have a volume of 3.45 cu cm. Each chamber is provided with two small threaded holes for filling and emptying. The filling holes may be sealed with stainless-steel screws. Drilled lengthwise through the center partition is a 0.250-in.-diam hole. Inserted into this hole is a rod having seven 0.059-in.-diam holes drilled radially through it. The total "hole" volume is 0.078 cu cm. When the rod is properly aligned, the holes in it constitute the "diaphragm" through which diffusion occurs. The center section was of Teflon and the rod and face plates were of Plexiglas. Four such cells were constructed and used in this study. Subsequent to this investigation, a similar cell constructed entirely of iron was fabricated and tested at higher temperatures. Several considerations led to this final design. It is desirable to minimize the volume of the cell chambers to decrease the time required for a measurement. However, the total volume of metal in the diaphragm must be small in comparison with that in the chambers. To facilitate filling and emptying it is desirable to have a diaphragm which may be closed.

Jan 1, 1970

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&apos;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.&apos; 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&apos;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&apos;&apos; and has been used to determine the thermodynamic data for Cu-Ni alloys.&apos; 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&apos;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.&apos; 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 H. J. French

WITHIN the past few years, particularly because of the rapid growth of the airplane industry during the war, considerable attention has been paid to the manufacture of light-wall cold-drawn seamless and welded steel tubing for structural purposes. While the manufacture of such tubing is not, in itself, a difficult matter, some difficulties have. been encountered in producing the same under specifications requiring definite physical properties. It is the purpose of this paper to describe the methods of manufacture and the properties that may be obtained by such methods for tubing coming within about ½ to 2 in. (12.7 to 50.8 mm.) outside diameter and 10 to 22 Birmingham wire gage (0.134 to 0.028 in. wall thickness). Such tubing is largely used as structural material in the aircraft industry, and it is of the utmost importance that the physical and chemical properties should be known, and also that the various factors entering into the manufacture should be under such control as to allow these properties to be varied and held within definite limits. In general, tubing may be divided into four classes: namely, specialty tubing, such as riveted-sheet or plate, lock jointed, etc.; brazed tubing; welded tubing; and seamless tubing. Welded tubing may be divided into hot product, such as lap welded and butt, welded, and cold product, such as acetylene and electric welded. Seamless tubing may be hot rolled or cold drawn.

Jan 9, 1919

By G. H. Matheson, J. M. W. Mackenzie

The flotation rate of coal has been studied using a continuous laboratory flotation cell and a multiple exposure photographic technique. The effects of particle size, reagent additions and cell turbulence on the flotation rate of coal have been investigated. The results have been analyzed in terms of current theories of particle bubble encounter and adhesion. The rupture forces which occur during particle bubble encounter have been shown to have an important effect on the flotation rate of coarse coal particles. The flotation of coal is a time dependent process, and in order to obtain a complete understanding of the operation it is necessary to determine the kinetics of the process. In coal flotation, the flotation rate and the associated values of cell productivity in terms of tons per kilowatt-hour and tons per cubic foot of cell volume are of greater importance than in most other mineral flotation operations. The reasons for this are associated with the low unit value of coal and the relatively high cost of coal flotation compared with other coal cleaning processes. An important aspect of coal flotation kinetics is the design of coal flotation cells. The cells used in many coal cleaning operations are often replicas of those used for the treatment of sulfide ores and are not necessarily suitable for the treatment of coal washing pulps, which usually contain a higher percentage of coarse and floatable material than the sulfide pulps for which the cells were designed. This disadvantage of many coal flotation cells has been recognized by Russian engineers who, by the addition of baffles to their subaeration coal flotation cells have increased the cell capacity by 100%. Investigation of the variables which influence flotation kinetics and cell productivity are, therefore, important to the coal industry where flotation is the only accepted method of cleaning the fine (-1/2mm) coal. The kinetics of the flotation process have been investigated in detail by Schumann10 who developed a continuous flotation cell which permitted the study of flotation under steady state conditions. This technique has been used by Gaudin et a1.,6 Brown and Smith and recently by Jowett and Savfi.7 The latter authors have developed a refined mathematical treatment for interpreting the results of continuous laboratory tests. Attempts have also been made to study flotation kinetics using conventional batch testing techniques. The experimental difficulties, however, and the problems of determining the order of the flotation rate process have made this technique of dubious value. A summary of the proposed rate equations for batch testing and the difficulties associated with this technique is given by Brown and Smith. 2 The experimental techniques described above are concerned with the rate of production of froth product. However, several authors, notably Sutherland, 11 Bogdanov1 and Philippoff, 9 have analyzed flotation

Jan 1, 1963

By R. W. Kraft, L. D. Graham

The process of&apos; spheroidization, or more properly coarsening, of Al-CuAl,eutectic alloy specimens with various initial microstructures was studied by quantitative metallographic and X-ray diffraction techniques. By measuring the rale at which specimens with a very fine dispersion of phases (produced by quenching molten droplets of the alloy in water) coarsened it uias determined that the rate-controlling mechanism for coarsening was diffusion, probably of aluminum in the aluminum-rich phase. The lamellae in specimens with a high degree of microstructural and cr-ystallog/uphic anisotropy (produced hy unidirectional solidification of ingots) thickened during heat treatment by recession of the CuAl, platelets from jaulted regzons, yet the specinlens retained a very high degree of. anisotropy after prolonged heat treatments at a temperature within 8°C of the eutectic temperature. In such specimens the crystallographic orientation relationship between the phases remained constant and no change in the crystallographic substructure occurred. Based on these observations a model was developed for the coarsening—or rate of&apos; thicken-ing—oj- the lamellar structures which predicts that the rate of decrease of interface area is proportional to the square of lamellar interface area. Experiments with degenerate and very coarse lamellar microstruc -tures preduced by extremely slow unidirectional solidification) indicate that initial microstructure is a most important factor governing the final micro-structure after heat treatment. The particle size and shape of dispersed phases are important parameters affecting the properties of a wide variety of two-phase materials. As is well-known, varietythe dispersed-phase particles tend to coarsen at appropriately high temperatures because the interface energy of the system is reduced by the concomitant reduction in interface area. The phenomenon of

Jan 1, 1967

By Lovell Lawrence

MAGNETITE deposits in the Eastern States have been mined uninterruptedly since pre-Revolutionary War days. The industry, thriving in normal times, was given impetus in all periods of tumult, and continued to advance and expand, until the Lake Superior ores came into production. A period of comparative quiet existed until increased freight rates, together with increased mining costs on Lake Region ores, permitted the magnetites again to compete. This, coupled with World War demands, created unpre¬cedented activity. Producing plants were at their peak, new mines were equipped and put in operation and the industry pushed production beyond the absorption point. Ore stocks were tremendous, internal competition severe, and a great increase in import of European ores brought the industry to a low ebb in 1923.

Jan 1, 1933

By R. L. Orr, J. D. G. Masse, Ralph Hultgren

The relative partial molar enthalpies of gold and tin in liquid Au-Sn alloys have been measured from Xsn = 0.474 to 0.510 at 696°K, slightly above the melting point of solid AuSn. Within an average precision of 6 cal per g-atom, the data are represented by two smooth curves, which satisfy the Gibbs-Duhem relationship and which do not show any anomalous behavior in the range of composition studied. The results give no support to the hypothesis that atomic associations in the equiatomic liquid alloy resemble those in solid AuSu. LITTLE has been firmly established as to the nature of atomic distribution in liquid metallic phases. A favored hypothesis assumes the existence of atomic groupings in the liquid phase which are similar to those in solid phases occurring at lower temperatures. Beginning with this hypothesis, it is often possible to adjust the values of certain parameters (such as degree of association) so that approximate agreement is achieved with certain features of the X-ray diffraction pattern of the liquid, even though many other possible structures might satisfy the data equally well. Thus, in this manner, the structure of liquid tin has been described as a dispersion of fragments of gray tin in a matrix of metallic tin.1 Four X-ray diffraction studies2"5 have been made of the liquid alloy of composition AuSn at temperatures slightly above the melting point of the solid. Each investigator concluded, on somewhat different grounds, that the liquid consisted to a large extent of arrays of atoms similar to the solid, with admixture of more disordered arrays. Solid AuSn has the nickel arsenide crystal structure: each tin atom has six nearest neighbors, all gold atoms; and each gold atom has six tin and two gold atoms as nearest neighbors. It remains highly ordered to the melting point. The liquid alloy has a large exothermic (?H700° K = -2700 cal per g-atom6) enthalpy of formation, favoring ordering and making the hypothetical molecular association not unreasonable. The possible existence of such solidlike arrays, or of a high degree of order that occurs preferentially at a specific composition in a liquid alloy, might also be revealed by thermodynamic behavior somewhat analogous to that in highly ordered solid alloy phases. The latter often exist over wide composition ranges, within which the highest degree of order occurs at the ideal composition for which the atomic fractions are equal to the fractions of sites which are "right" for each kind of atom. On departing from the ideal composition, the excess atoms occupy "wrong" positions, raising the internal energy and making it progressively easier for additional atoms to occupy "wrong" positions. Thus, on either side of the ideal composition, there should be a pronounced rise in the entropy and enthalpy, which would be shown particularly by the change in the relative partial molar enthalpies, ?Hi, since they depend strongly on d?H/dx. In the one case where accurate measurements have been made, the solid AuCu ordered phase, the structure becomes much less ordered as the composition deviates from the ideal, and relative partial molar enthalpies change sharply as shown by the data6 given in Table I. This suggests the possibility of finding similar pronounced changes in the relative partial molar enthalpies of gold and tin in liquid alloys near the composition AuSn if the postulated solidlike ar-

Jan 1, 1967