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By P. Douglas, G. M. Leak, B. Mills

The sinusoidal surface relaxation technique has been used to measure the surface self-diffusion coefficient of spectroscopically pure nickel over a wide temperature range under a hydrogen atmosphere. A kink in the Arrhenius plot has been observed. In the temperature range T/T 0.98 to 0.80 (T in O K and T, is the melting temperature) the average self diffusion coefficient is given by Below the temperature T/T,- 0.80a decrease in the slope of the log Ds us 1/T plot is observed. This is associated with a diffusion process characterized by a lower activation energy (-20,000 cal mole'') and smaller preexponential term (-10- sq cm sec"). A series of experiments were carried out at T/Tm = 0.61 under a hydrogen atmosphere of higher oxygen partial pressure than for the rest of the experiments. It was found that Ds was significantly depressed due to oxygen adsorption. This evidence supports the opinion that the low temperature process (activation energy -20,000 cal mole-') is unlikely to be due to oxygen adsorption. An interesting feature of the present data is that the transition temperature (T/Tm - 0.80) is a function of orientation. For a small number of crystals of measured orientation the transition temperature was observed to be higher towards the low index (100) pole. Theories of surface diffusion are briefly reviewed and it is concluded that the present reszuts are best explained by invoking a surface roughening process. GJOSTEIN has recently analyzed available surface diffusion data for a wide range of metals. He suggested that two mechanisms were operative for fcc metals, an adatom process at high temperatures and a vacancy process at low temperatures. Results for nickel can be summarized as follows. At low temperatures (T/T, - 0.3 to 0.44) under ultra high vacuum conditions, Melmed2 measured an activation energy Q of 21 kcal mole-' using field electron emission microscopy. At higher temperatures (T/T - 0.7 to 0.9) under a vacuum of 10- ' torr, Maiya and lakel measured y as 39 kcal mole-' using the multiple scratch smoothing technique. The present work was undertaken to try to find out if two distinct processes could be observed. High temperature results give Q about 47 kcal mole-': there is evidence also for a low temperature value of about 20 kcal mole-'. These measurements were all made under a hydrogen atmosphere, in the temperature range 860" to 1412°C. Concurrent with the present study Bonze1 and jostein> have also observed a break in the Arrhenius plot for the (110) surface of nickel. These measure- ments under ultrahigh vacuum conditions using the laser diffraction technique are in excellent agreement with the work reported here under hydrogen annealing conditions. THEORY The available surface relaxation techniques include single and multiple scratch smoothing and grain boundary grooving. The processes have been compared in detail by Gjostein for conditions where surface diffusion dominates6 and Mills et al? where volume diffusion dominates. In summary the relevant points are as follows. Grain boundary grooving gives an average Ds for the two surfaces adjacent to the boundary and this can, to some extent, be simplified by using symmetrical bicrystals. This technique has been used to study the effect of environment on Ds for silver and copper.'-'' Scratch techniques yield Ds values for the small orientation range exposed by the scratches (-2 deg). The multiple scratch process is preferable because the profile rapidly becomes sinusoidal and can then be interpreted theoretically in a relatively simple way. Also corrections for mass transport processes other than surface diffusion can be introduced easily. Mullins" considered a sinusoidal profile described the wavelength of the profile. After time t the profile can be described by the equation The terms A, A', C, and B which account, respectively, for contributions due to evaporation-condensation, diffusion through the gas phase, volume diffusion through the lattice, and surface diffusion are defined as: where Ds = the surface self diffusion coefficient ys = the surface energy per unit area p = the equilibrium vapor pressure over a flat surface pa = the equilibrium vapor density over a flat surface DG= the diffusion coefficient of vapor molecules in the inert gas DM = the mass transfer diffusion coefficient which for a pure cubic metal is Dv/f where Dv is the radiotracer diffusion coefficient and f is the correlation factor H = the molecular volume V = the surface density of atoms, il2'3 M = mass of an evaporating molecule

Jan 1, 1970

By ALFRED KAUFFMAN

NO matter what position we hold, workman, foreman, superintendent, manager, president, or what not, let us fail to give or to make good products, then see how quickly we'll be called to account for- our work by the buying public. The waves of progress taught us that millions were wasted in unnecessary strikes-we also learned that many losses were due to neglect on the part of manufacturers to give the same consideration and attention to the human element of their factory as they gave to their machinery. The employees learned also that the employer was their agent who found purchasers for the product of their labor. So between the two we learned that many years of labor were needed in order for a worker to recover his wasted savings, or for the manu¬facturer to replenish his loss. Treat 'em rough, and tell 'em nothing, was not very far from the true relationship between management and employees in manufacturing plants in the early days. Today just exactly the opposite views are held by executives whose function is the handling of employees. Men today want to know what it is all about. They are intelligent enough to comprehend the facts, and to use them constructively, and it is good business to give them the information.

Jan 1, 1929

By M. H. Caron

THE most outstanding property of ammonia liquors, used in the ammonia leaching process is their very limited ability to dissolve all compounds present in reduced ore except nickel and cobalt. Although they do have such a high degree of purity, even the smallest amounts of impurities contaminate the precipitate of basic nickel carbonate that may be obtained from pregnant liquors by straight distillation. Figures have been given in a separate paper regarding the extent of such contamination. The product of straight distillation is likely to contain small amounts of Fe, Mn, MgO and SiO2 as well as some sulphate and sulphide. The sulphur can be readily eliminated by calcination of the product at the proper temperature and MgO and SiO2 by reduction and melting of the metal with a suitable flux. After such treatment the metal is relatively pure, and the iron and manganese content will be very small. The cobalt content, however, may vary considerably, depending upon the ore treated. The metal obtained from pure true garni-erite ores usually has only a small cobalt content of less than 1 pct. Metal obtained from medium grade iron-rich nickel ores may show cobalt values from 2 to 3 pct, and the alloy obtained from laterite is likely to contain as much as 10 pct cobalt. By proper treatment a good deal of cobalt may be recovered from lateritic nickeliferous iron ores, and cobalt will become the major constituent of the pregnant liquor if asbolan ores or similar products are treated. The pregnant liquor of "run of mine" nickel ores may have a pinkish shade, indicating the presence of cobalt. It is evident that from such liquors the metals should be recovered separately. Even if cobalt is present in only very small amounts, it would probably be economically justifiable to recover both metals as pure as possible if a suitable process could be devised. The author has made investigations along this line and has patented some processes adapted to the treatment of this type of solutions. Selective Dissolution of Nickel from Basic Nickel Carbonate Containing Some Cobalt: Basic nickel carbonate obtained from true garnierite ores by straight distillation of the pregnant liquors, always contains some cobalt as well as the normal impurities. In. order to improve the quality of the nickel product and to recover most of the cobalt, the following process has been devised. By using liquors with a low CO2 to NH3 ratio, nickel can be redis-solved preferentially to cobalt. It is not a sharp and clean separation but a selective one, for the bulk of the nickel may be redissolved with a small amount of cobalt, and a small residue may hold the bulk of the cobalt. The greatly increased cobalt content of the residue is indicated by a pronounced olive green color, in contrast with the light green color of pure basic nickel carbonate. The following example is given from Dutch patent No. 52788, Klasse 40a. 43 granted June 17, 1942: The original precipitate contained about 0.55 pct cobalt calculated on total nickel + cobalt. Eight hundred and fifty grams of the basic nickel carbonate were redissolved in leach liquor containing 7.12 pct NH3 and 2.12 pct CO2. The weight of the dry residue was about 3.5 pct of the original weight. By analysis it was found that the residue contained: Fe 1.93 pct, Co 6.01 pct, Ni 34.87 pct and also a certain amount of silica. The clear filtered blue liquor was distilled and the precipitate of basic nickel carbonate from this analyzed: Fe 0.008 pct, Co 0.0146 pct, Ni 42.37 pct. It is obvious that this product is considerably more pure, since calculation shows that about 94 pct of the original cobalt remained in the residue. Cobalt and nickel can be recovered by further

Jan 1, 1951

By G. Meyrick, H. W. Paxton

Observations on the tensile deformation of single crystals of austenitic stainless steels as a function of composition, orientation, and temperature are described and compared with relevant data for other alloys. Crystals free from second phases show sharp yield points followed by Lüders' extensions of up to 20 pct. The critical resolved shear stress is strongly temperature-dependent increasing fourfold between 423O and 77°K. A temperature-independent low rate of hardening follows the Luders' extension and is frequently associated with overshoot. Unlike pure metals where Proficse cross slip usually occurs at the end of linear hardening, this stage is terminated either by cross slip or by slip on the conjugate system, the particular node apparently depending upon initial orientation and composition. The presence of 6 ferrite or martensite has a profound effect upon the magnitude of the yield stress and the shape of the stress-strain curve. In experiments on transgranular-stress corrosion cracking of austenitic stainless steels in boiling magnesium chloride, several workers1'2 have shown that increasing amounts of nickel tend to reduce the probability of specimen failure. Reed and paxton3 have observed in single crystals that the macroscopic crack plane changes as the nickel content is increased. For 18 pct Cr-8 pct Ni, the crack plane is sensibly perpendicular to the applied tensile stress; for 20 pct Cr-20 pct Ni the crack plane is (100). The average crack-propagation speed is much lower in the 20 pct Ni crystals. Furthermore, the possible importance of stack-ing-fault energy in nucleation and growth of cracks has been suggested by a number of workers. While the general effect of variations in stack ing-fault energy appears to be quite well-correlated with observed variations in cracking characteristics, each of the theories assigns rather different detailed reasons for these effects. Because the stack ing-fault energy of austenitic steels is believed to be increased with increasing nickel content, and because some theories of trans-granular cracking postulate a mechanical stage in the crack propagation (rather than relying entirely on electrochemical solution), it appeared to be of some interest to investigate the mechanical properties of a series of different compositions of aus-tenite single crystals. These experiments were considered of intrinsic value in view of the relative scarcity of such data on fcc alloys. This paper gives the results of some experiments carried out with this aim in mind, and suggests various 'other experiments which may be helpful in future studies. The experiments are also of interest in view of the recent interest in obtaining higher-strength steels by control of the imperfection content of austenite; although the compositions are not directly comparable, the results are still probably valuable. Comparisons with experiments on other fcc alloy crystals are made where possible to see how well the general pattern of behavior is understood. EXPERIMENTAL PROCEDURE The alloys used in this investigation were vacuum-melted heats of nominally 20 pet Cr-20 pet Ni-60 pet Fe, 20pctCr-16 pct Ni-64 pct Fe, and 20 pctCr-12 pet Ni-68 pet Fe.* Analyses of the material are

Jan 1, 1964

By E. Buehler, H. J. Levinstein

The temperature ranges in which the three inter-metallic phases in the Nb-Sn system form have been determined and the composition and structure of two of the three phases has been established. The kinetics of the formation of Nb3Sn in cored wire samples has been studied in the temperature range of 800° to 1050°C. From 800°to 950°C the rate of formation increases by four orders of magnitude. The rate-controlling step for the formation process in this temperature range appears to be the diffilsion of tin through NbSn. At higher temperatu~es a change occurs in the mechanism of the formation process such that up to a temperature of 1050°C the rate of formation of Nb3Sn does not increase above the rate observed at 950°C. For temperatures helow 950°C the current-carrying capacity of the wire increases with increased percent reaction reaching a maximum value when the formation process is 90 to 95 pct complete. The maximum current-carrying capacity obtainable in this temperature range is independent of the temperature. Above 950°C tlze current-carrying capacity obtainable in the wire decreases with increasing temperature of formation. A model is proposed which accounts for the ohserved behavior. RECENTLY, Buehler et a1.l reported the results of an investigation of the process variables which influence the superconducting properties of Nb3Sn-cored wire. These results indicated that at least four variables affect the properties of the manufactured wire. These include composition, particle size of the starting powder mix, temperature of heat treatment, and time of heat treatment. In order to understand completely the role of these variables, it is necessary to have an accurate knowledge of the phase equilibria in the Nb-Sn system. At the present time, phase-equilibrium diagrams for the Nb-Sn system have been published by a number of investigators.2-5 The diagrams differ as to the number of phases present, the composition of the phases, and the temperature range of stability of the phases. The present investigation was undertaken in order to resolve these differences. Since the investigation of Buehler et al. demon- strated that the length of time at the temperature of heat treatment affected the superconducting properties of Nb3Sn, it is apparent that it is necessary to understand the kinetics of the formation process as well as the equilibrium conditions before a complete understanding of the system is possible. As a result, the kinetics of formation of the various phases in the system were also studied in this investigation. EXPEFUMENTAL PROCEDURE Diffusion couples and sintered powdered compacts were employed in the phase-diagram investigation. The diffusion couples were made by filling 1/8-in.-ID monel-sheathed niobium tubes with tin. The monel sheath was employed to facilitate drawing.' The tubes were then drawn to a tin-core diameter of 32 mils. Samples approximately 3 in. long were then cut from the drawn composite. The tin was drilled out of the ends to a depth of 1/4 in. and niobium-wire plugs were inserted into the ends and peened over. The monel was removed by etching in concentrated nitric acid, after which the samples were sealed in evacuated quartz bulbs and heat-treated in a resistance-wound tube furnace. The samples were quenched into ice water upon removal from the furnace. The diffusion couple samples were examined metallographically employing a chemical etching solution consisting of 10 ml of saturated chromic acid per g of NaF. In addition, two anodizing solutions were used for phase-identification purposes. The first was the picklesimer7 solution; the second consisted of equal parts by volume of 30 pct H2O2 and concentrated NH4OH to which 1 g of NaF was added per 25 ml of solution. The anodizing conditions for the second solution were 2 v and 100 ma with a tin cathode. The powdered compacts were made by pressing previously mixed powders of 99.9 pct pure Sn and 99.6 pct pure Nb supplied by the United Mineral Co. into cylinders 3/8 in. in diameter by 1/2 in. long. The cylinders were then sealed in quartz tubes and heat-treated in the same manner as the diffusion couples. The samples were examined metallographically and by X-ray diffraction techniques. Since it was desirable to be able to correlate the kinetic data with current-carrying capacity, the type of specimen chosen for this part of the investigation had to be a compromise between the optimum system for studying kinetics and one which was suitable for making current-carrying capacity

Jan 1, 1964

By J. Kent Smith

THE object of this investigation was to ascertain the effect of varying percentages of beryllium upon pure copper and the properties of the resultant alloys in their softest condition, the effect of heat hardening on them, and the extents to which these properties could be augmented by different combinations of heat hardening and cold rolling. The data compiled in this paper represent partial results of continuing work done by the writer during the years 1930 and 1931, which was a continuation of the unpublished ground work incepted in the laboratory of the Beryllium Corporation of America by H. B. Pulsifer in the year 1926. A short bibliography on beryllium alloys is appended to this paper. It has, of course, long been known that copper subjected to cold work is hardened and strengthened to a considerable extent, furthermore it had been qualitatively noted in previous experiments that copper-beryllium alloys seemed to take on hardness and strength as the result of cold work at a greater rate even than does plain copper. It was decided therefore to endeavor quantitatively to determine such rate of increase, as also the relative increases by combinations of cold working and heat hardening. The results are summarized in Tables 3, 4 and 5. A preliminary series of experiments had indicated that by an exposure to the heat of 575° F. for 2 1/2 hr. age-hardening of a 2.50 per cent beryllium-copper alloy took place. Slab ingots of nine different beryllium-copper alloys were prepared under identical conditions by means of the addition of a previously prepared 12.5 per cent beryllium-copper alloy to well melted and deoxidized pure copper. The ingots were then reduced by hot rolling to 12 gage (about 0.080 in.). These strips were heated to 1450° F. and quenched in cold water, and thus brought to their softest condition. (See Table 1.) Strips were next "precipitation-hardened" by reheating to a definite temperature. Similar strips to those itemized in Table 1 (which had been quenched from 1450° F.) were reheated for varying periods of time at 575° F. The hardness figures show that a metastable condition, of which the range of stability is dependent entirely upon time at the given temperature, begins to be noted in copper samples containing as little as 0.85 per cent beryllium. It is extremely noticeable in samples containing

Jan 1, 1932

By R. G. Ward, John Henderson. R. G. Hudson, G. Derge

Densities of melts of the iron oxide-silica system in contact with solid iron have been measured by the maximum hubble pressure method in the composition range O to 37 wt pct SiOz and the temperature range 1255 to 1410C. The constitution of the melts is discussed and it is postulated that the structure changes from a dislribution of iron ions in an oxygen ion network at pure "FeO" to a distribution. of iron ions in a network of silicate tetrahedra at the orthosilicate composition. JOHN HENDERSON, Junior Member AIME, was formerly with the Metals Research Loborotory, Carnegie Institute of Technology, Pittsburgh, Pa., on leave from Broken Hill Proprietary Co., Ltd., Research Division, Shortland, Australia. R. G. HUDSON, formerly with Metals Research Laboratory, is now with the John Jay Hopkins Loborotory for Pure and Applied Science, General Atomic Division, General Dynamics Corp., LaJolla, Calif. R. G. WARD, was formerly with the Department of Metal lurgical Engineering, Carnegie lnstitute of Technology, while on leave from the Department of Metallurgy, University of Sheffield, England. G. DERGE, Member AIME, is Jones and Laughlin Professor of Metallurgical Engineering, Carnegie lnstitute of Technology. Manuscript submitted January 19, 1961. ISD The system iron oxide-silica is an important one metallurgically because it forms the basis of several complex slag systems in use for industrial smelting and refining processes. In recent years considerable work has been done on liquids of this system but there are still many points of difference among workers using different experimental techniques and theoretical approaches. Phase equilibria/"3 activity,4-6 electrical conductivity,' current efficiency,' transference number,8 viscosity,9 surface tension,'' and density" measurements have all contributed to an understanding of the problem. Measurement of density is one procedure which is directly indicative of liquid structure since any deviation from ideality must be a result of structural interactions. Liquids of the iron oxide-silica system are of special interest because this is one of the few metal oxide-silica systems on which measurements can be carried out conveniently over the entire composition range from pure oxide to silica saturation. This includes the range of high basicity which has received relatively little attention in other systems. Although one investigation of density in this system has previously been undertaken," the results seem of sufficient importance to warrant the independent redeter-mination reported here.

Jan 1, 1962

By R. W. Heckel, R. L. DeGregorio

The DeHoff method of determining the size distribution of ellipsoid-shaped, second-phase particles has been applied to the spheroidization of cementite in a eutectoid steel. The surface area of Precipitates determined from the various size fractions in the distribution was correlated with surface-area measurements based on the number of intersected interfaces on a random lest line. The precipitate particles were found to be oblate ellipsoids with an axial ratio of about 0.90. The size distributions were found to be log-normal. A method is proposed whereby the shrinkage of small particles and growth of large ones can be determined from the experimental data. The experimental data are compared to previously proposed mathematical models describing diffusion-controlled kinetics and various types of interface-controlled kinetics. The experimental growth and shrinkage rates are considerably slower than those predicted by diffusion-controlled kinetics. The best fit is obtained for a model describing interface-controlled kinetics limited by the rate of formation of cementite at the growing interfaces where the interfacial reaction rate is proportional to the solute thermodynamic activity gradient across the surface. THE subject of spheroidization of second-phase particles has been considered previously by other investigators. Livingston1 has studied the precipitation of the cobalt-rich phase from copper alloys containing 0.7 to 3.2 wt pet Co. His results indicate that the average particle size increases as the cube root of the heat treatment time in accord with diffusion-controlled kinetics.'-' Komatsu and rant' in their studies of the growth of SiO2 in a dispersion-strengthened copper-silica alloy found that the initial growth of SiO2 proceeded by diffusion-controlled growth and later stages were limited by interface-controlled growth. The values of the activation energy obtained for the interface- controlled process led them to the conclusion that the process was limited by the dissociation of SiO2 at the shrinking interface. The transition from diffusion-controlled growth to interface-controlled growth was characterized by a particle size which varied with the heat-treatment temperature. It is also interesting to note that the particle-size distribution as found by Komatsu and Grant exhibits log-normal behavior when replotted on log-probability coordinates. Dromsky, Lenel, and Ansell9 have observed the growth of Al2O3 particles having a mean free path of about 1.5 to 13 µ. Their photomicrographs indicate that the Al2O3 particle sizes were larger than those observed by Komatsu and Grant. Dromsky, Lenel, and Ansell concluded that the Al2O3 coarsened by an interface-controlled growth mechanism limited by the solution of A12O3 at the shrinking interfaces. Bannyh, Modin, and Modin10 have studied the spheroidization of a eutectoid steel (0.83 wt pet C). Their spheroidization (tempering) treatments were carried out in the range from 210o to 700°C for times between 1.5 sec and 20 hr. Measurements of mean particle size as a function of time indicated a cube root of time dependence of size at 700°C, in agreement with previous analyses of diffusion-controlled kinetics.2°7 At lower temperatures, the time dependence was less than the one-third power. It is important to note that, although mathematical models of growth* considering particle-size distribution have been available, measurements of only mean particle size have been carried out. DeHoff11 has presented a quantitative metallography technique which is applicable to the determination of the size distribution of ellipsoids of constant shape. This method is applicable to both oblate and prolate ellipsoids of all ratios of minor to major axis and is based upon an extension of Saltykov's analysis12 of the distribution of spheres of varying size. DeHoff's analysis is based upon measurements of the minor axis of the particles on a random plane of polish in a unit area. This method provides a measure of the number of ellipsoids in various size ranges per unit area. As pointed out by DeHoff, such measurements may be used to obtain surface area and total precipitate volume data. Thus, the accuracy of the distribution analysis may be checked by comparison of the surface and volume

Jan 1, 1965

By P. B. Bucky

In previous publications1 it was shown that a scalar model of any weighty structure, where the stresses produced are mainly due to gravitational forces, will behave similarly to its prototype if the model and prototype material are the same and the model is placed in a centrifugal field of force (substituted for the gravitational field) which has been increased in the same proportion as the linear model scale is decreased. This principle is now being applied to a study of the behavior of mine structures in an attempt to determine the laws that control them. The importance of using models as a means of solving mining problems has been discussed previously, yet it may be well to reiterate here that this method of research and type of solution have been productive of far-reaching results in other engineering fields, notably those of hydraulics and aerodynamics. Model research is a comparatively cheap and time-saving method of checking practical experience. Up to the present time the best guide to what will happen underground has been the judgment of the man who has observed most and been longest acquainted with the local conditions. His experimental work underground is limited by the elements of cost, time and danger, while failure is seldom permissible. In a model, as in a test tube, all elements that affect the solution of a problem are under definite control. Each element may be varied independently at hill and its effects noted. Experimental work on a small-scale model may therefore be performed at a comparatively small expenditure of time and money, instead of on a full scale in the mine, where the cost, time, and danger elements are necessarily great. The experiments described in this paper are to be considered as part of a progress report and a continuation of Technical Paper 425. One object of the research program is to make each experiment point the way for further research on that particular phase of the general problem. The results and conclusions presented here are therefore not to be considered as final, but arc to be interpreted as

Jan 1, 1934

By Leonard C. Grimshaw

Diffusion of carbon from gases into iron has been the object of much research, because of its long recognized importance in carburizing processes, but the direct diffusion of carbon from steel into iron has received relatively little attention. Because of the increasing use of clad metals in industry, direct diffusion from steel into iron is becoming of practical importance. Therefore, the object of this investigation was to study the diffusion of carbon from several different kinds of steel directly into relatively pure iron, realizing that elements in the steels other than carbon might influence the rate of carbon diffusion. The previous work on diffusion of carbon into iron has been considerable, and includes many reports in foreign languages. This work has recently been well reviewed by Mehll and Krynitsky12 and the reader is referred to their excellent bibliographies. Methods of Study There are two main methods by which the direct diffusion of carbon from steel into iron may be studied. In one method, steel is first decar-burized in part, and diffusion of carbon then allowed to take place from the steel into the decarburized steel. This method is open to two serious objections: (1) the decarburized steel is not iron, but contains elements such as manganese, silicon, chromium or tungsten, which may be an essential part of the steel under study, and which may seriously influence the diffusion of carbon into the decarburized area; (2) there is from the start of diffusion an unknown carbon-concentration gradient between the steel and the decarburized area. Another method, which possesses neither of these disadvantages, is to study diffusion from steel into a thick plating of electrolytic iron. Herc the chief difficulty is to secure an electrolytic deposit of iron upon steel without introducing an oxide film at the interface that will interfere with diffusion. The author is able to deposit iron upon any kind of steel without introducing an oxide film at the interface, so that diffusion of elements from the steel into the iron is free to proceed unhindered.

Jan 1, 1938

By Leonard C. Grimshaw

Diffusion of carbon from gases into iron has been the object of much research, because of its long recognized importance in carburizing processes, but the direct diffusion of carbon from steel into iron has received relatively little attention. Because of the increasing use of clad metals in industry, direct diffusion from steel into iron is becoming of practical importance. Therefore, the object of this investigation was to study the diffusion of carbon from several different kinds of steel directly into relatively pure iron, realizing that elements in the steels other than carbon might influence the rate of carbon diffusion. The previous work on diffusion of carbon into iron has been considerable, and includes many reports in foreign languages. This work has recently been well reviewed by Mehll and Krynitsky12 and the reader is referred to their excellent bibliographies. Methods of Study There are two main methods by which the direct diffusion of carbon from steel into iron may be studied. In one method, steel is first decar-burized in part, and diffusion of carbon then allowed to take place from the steel into the decarburized steel. This method is open to two serious objections: (1) the decarburized steel is not iron, but contains elements such as manganese, silicon, chromium or tungsten, which may be an essential part of the steel under study, and which may seriously influence the diffusion of carbon into the decarburized area; (2) there is from the start of diffusion an unknown carbon-concentration gradient between the steel and the decarburized area. Another method, which possesses neither of these disadvantages, is to study diffusion from steel into a thick plating of electrolytic iron. Herc the chief difficulty is to secure an electrolytic deposit of iron upon steel without introducing an oxide film at the interface that will interfere with diffusion. The author is able to deposit iron upon any kind of steel without introducing an oxide film at the interface, so that diffusion of elements from the steel into the iron is free to proceed unhindered.

Jan 1, 1938

By Charles White Merrill

Mankind's progress is measured in minerals. Man's emergence from prehistory is marked by passage through a Stone Age and a Bronze Age and into the present era, sometimes called the Iron Age or the Age of Metals. With the evolution of civilization and the development of a modem industrial economy, minerals become more and more important. Structures, roads, and machines are built largely of minerals; the energy to heat the structures and to drive the machines is mostly mineral; agricultural fertility is maintained by mineral fertilizers and water; and military strength is provided by fortresses, armaments, and munitions, largely of mineral origin. Thus in the material world, in the productivity of the economy, access to minerals has paramount importance. Every evidence indicates increasing dependence on minerals in the modem economy, particularly on the mineral fuels as energy sources to provide the power base for advancing industrialization. Both the total and the per capita consumption of almost every mineral is increasing in the industrialized nations. Moreover, nations with predominantly agrarian economies call themselves underdeveloped and universally strive to industrialize. Most mineral consumption trends in the more advanced economies have been greatly exceeding population growth-which itself has been advancing at an accelerating rate--and sometimes have surpassed the growth in real income. Some minerals have only recently been adopted or grown to importance in use. Titanium as a metal appeared as a commercial product only in 1948, and even coal seriously displaced wood as a source of heat less than two centuries ago. On the other hand, minerals have always played an important role in construction. The prehistoric megaliths that form the dolmens of Salisbury Plain are stone; the pyramids are andesite faced with limestone; and many other ancient structures are built of mineral materials. In modem times the whole course of architecture has been redirected by new building materials, mostly mineral. Most conspicuous is the sky-

Jan 1, 1959

By R. S. Archer

THE PROPER representation of equilibria involving graphitic carbon in the constitutional diagram of the iron-carbon system is admittedly an unsolved problem. The complete solution of the problem will probably require the establishment of more experimental evidence than is at this time available. The object of this paper is to present the author's observations on some of the phenomena in question and his interpretation of this and other recorded evidence. The chief of the recently disputed questions upon which the author has experimental evidence concerns the occurrence of graphitization at temperatures below the A1 point. In a paper1 presented at the September, 1919, meeting of this Institute, the following is found: "the results given would seem to indicate that the graphite eutectoid lies at a smaller value of carbon content than has been previously supposed. At least this is true unless there is either a marked formation of graphite eutectoid at these rates of cooling, or a decomposition of pearlite into graphite, both rather unlikely suppositions, but not impossible ones." In a discussion of this paper, H. A. Schwartz2 takes the position that the possibility of graphitization occurring below the A 1 point is an open question, but that complete graphitization (to less than 0.10 per cent. combined carbon) commonly occurs above this temperature. Another opinion from the malleable castings industry is found in a recent paper3 by Touceda: "Also the carbide of iron can be broken up into its two soft constituents at the temperature referred to. This temperature is called the critical temperature, or critical range, and for air-furnace hard-iron castings it is in the vicinity of 1440° F. It is the

Jan 2, 1920

By H. A. Coy, James A. Noble

The Mascot mines of the American Zinc Co. of Tennessee are situated at Mascot, Tenn., 14 miles northeast of Knoxville, on the Southern Railway. The district is centrally located in the Great Valley, or Appalachian Valley Province. Prior to 1900, a small output of zinc was obtained from oxidized ore mined in open pits. In 1900, a shaft was sunk to sulfide ore, and in 1903, a second shaft was put down, neither being as deep as 200 ft. The American Zinc Co. of Tennessee began drilling in 1911, and outlined an ore-body to which its No. 1 shaft was sunk, to a depth of 365 ft. Since that time, the American Zinc Co. of Tennessee has been the only operator in the district. The Federal mining laws have never been in operation in Tennessee and mining lands are as irregular in boundary and area as farm lands. Ownerships are generally held in fee. In most cases the surface and mineral rights are transferred together. Electric power is supplied at 66,000 volts by the Tennessee Power Co., from a hydro-electric plant at Parksville, Polk County, Tenn., 100 miles from Mascot. No other power is used, but an emergency steam plant is held ready in case of interruption of service. Labor is all native and non-union. Negroes are employed for most of the shoveling, and for a few miscellaneous jobs, but for almost no other work. Exploration Exploration is carried ahead of mining largely by surface drilling. Both churn and diamond drills are used. Holes are not spotted according to geometric plan, but to block out ore outlines with the least number of holes. Churn-drill cuttings from each 5-ft. run are mounted for formation record, and in ore ground, all the bailings from each 3 ft. of advance are sampled and assayed. Diamond-drill cores are sampled and a specimen core filed for formation record. In ore ground, all the core

Jan 1, 1925

By F. C. Langenberg

It is the purpose of this paper to present a limited amount of experimental data obtained on the Charpy impact machine. Several concrete examples will be given showing the relation existing between the results obtained upon the Charpy impact machine and the behavior of the parts tested when in service. Although it is pointed out by G. Charpy and A. Cornu-Thenard1 that it is first necessary to determine a satisfactory working process before studying the correlation between the results of these tests and the behavior of the parts tested in service, this ideal course cannot be strictly adhered to. If a certain part repeatedly fails in service and the available tests give no indication of its cause, advantage must be taken of any possible means that will solve the problem; therefore, even though the reliability of the results obtained by the Charpy impact machine have been questioned by many, it was necessary to use this instrument without giving careful consideration to its possible sources of error. It would seem that the conclusions arrived at by Charpy -and Cornu-Thenard justify the assumption that the precision obtained by this machine is comparable to that obtained by the other more common forms of testing. The second general conclusion arrived at by them, namely, that the impact test upon notching does not offer any direct correlation to the ordinary tests, is also borne out by many hundred determinations made in the laboratories at Watertown Arsenal. This statement, however, should be qualified as follows: Other ordinary tests include the static tensile test from bars taken in a longitudinal direction and the Brinell hardness. The author agrees that no law is yet known for the computation of the energy absorbed in the rupture of bars of the same material but of different dimensions. Although Charpy and Cofnu-Thenard do not refer in their valuable article to the use of the Charpy machine in industrial practice, it should be stated that this instrument has been in constant use in the laboratory at Watertown Arsenal for several years, and is now employed for both routine and experimental testing.

Jan 1, 1920

By J. K. Stanley, R. F. Meel

The recrystallization of cold-worked metals is studied ordinarily by determining the temperatures required for complete recrystallization to occur within a given arbitrary time period, usually within 15 min. to 2 hr. The results obtained are conventionally assembled in a three-dimensional diagram relating this temperature to the amount of cold-work (percentage deformation) and the resultant grain size, though sometimes other modes of representation are emp1oyed.l Such three-dimensional diagrams are not complete, for the number of variables exceeds the number represented. The process of recrystallization is characterized by a time-rate, a fact that is not portrayed upon ordinary recrystallization diagrams. It is known that recrystallization consists in the formation of new nuclei and the growth of these nuclei, a process that continues until the matrix is completely consumed and the original set of grains entirely replaced by the new. This knowledge is old.2 Truly heterogeneous reactions invariably proceed by nucleation and growth; the decomposition of eutectoid solid solutions provides an example about which much is known,3 and freezing, originally studied by Tammann, provides the classic example. Although recrystal- lization is not a heterogeneous reaction within the orthodox meaning of the term, the mechanism of the process is the same. As in eutectoid inversion and freezing, it should be possible to study the rate of isothermal recrystallization as a function of time, and it should also be possible to analyze the isothermal reaction curve into the component rates of nucleation and growth that determine them.* Other methods, not employing the rates of nucleation and growth, have been used to represent the rates of such reactions, but these in general have been artificial and have not led to progress. 4,5 The theory of recrystallization is not in advanced state; if recrystallization data were obtained in terms of the rate of isothermal recrystallization, and in terms of the rate of nucleation and the rate of growth of recrystallized grains, and in particular if the temperature coefficients of these rates were measured accurately, an adequate theory should be more readily developed.27 Such an effort requires proper experimental technique, but especially requires suitable methods of mathematical analysis to convert mcasurements made upon a surface of polish into values for the rate of nucleation and the rate of growth and to combine these into a rate of isothermal recrystallization. These methods are now available for the case of three-dimensional recrystallization (recrystallization of

Jan 1, 1942

By R. F. Meel, J. K. Stanley

The recrystallization of cold-worked metals is studied ordinarily by determining the temperatures required for complete recrystallization to occur within a given arbitrary time period, usually within 15 min. to 2 hr. The results obtained are conventionally assembled in a three-dimensional diagram relating this temperature to the amount of cold-work (percentage deformation) and the resultant grain size, though sometimes other modes of representation are emp1oyed.l Such three-dimensional diagrams are not complete, for the number of variables exceeds the number represented. The process of recrystallization is characterized by a time-rate, a fact that is not portrayed upon ordinary recrystallization diagrams. It is known that recrystallization consists in the formation of new nuclei and the growth of these nuclei, a process that continues until the matrix is completely consumed and the original set of grains entirely replaced by the new. This knowledge is old.2 Truly heterogeneous reactions invariably proceed by nucleation and growth; the decomposition of eutectoid solid solutions provides an example about which much is known,3 and freezing, originally studied by Tammann, provides the classic example. Although recrystal- lization is not a heterogeneous reaction within the orthodox meaning of the term, the mechanism of the process is the same. As in eutectoid inversion and freezing, it should be possible to study the rate of isothermal recrystallization as a function of time, and it should also be possible to analyze the isothermal reaction curve into the component rates of nucleation and growth that determine them.* Other methods, not employing the rates of nucleation and growth, have been used to represent the rates of such reactions, but these in general have been artificial and have not led to progress. 4,5 The theory of recrystallization is not in advanced state; if recrystallization data were obtained in terms of the rate of isothermal recrystallization, and in terms of the rate of nucleation and the rate of growth of recrystallized grains, and in particular if the temperature coefficients of these rates were measured accurately, an adequate theory should be more readily developed.27 Such an effort requires proper experimental technique, but especially requires suitable methods of mathematical analysis to convert mcasurements made upon a surface of polish into values for the rate of nucleation and the rate of growth and to combine these into a rate of isothermal recrystallization. These methods are now available for the case of three-dimensional recrystallization (recrystallization of

Jan 1, 1942

By Oren C. Baptist, Carlon S. Land

Laboratory research has been conducted to evaluute the effect of clay hydration on the permeability to gas of water-sensitive reservoir sands. Samples of a .sandstone containing trace amounts of montmorillonite and a sample of montmorillonite were .studied in the laboratory to detertnine whether swelling or dispersion was the cause of permeability reduction in these samples. Heliuin, containing various amounts of water vapor, was used to hydrate the clay minerals and to determine the gas permeability at various stages of clay hydration. The amount of water adsorbed by the samples using this method is small. The nonwetting-phase permeability at higher water saturations war investigated by saturating the with water and measuring the permeability to humid helium while decreasing the water saturation, Relative-permeability curves obtained from results of these procedures were used to estimate the effect of the swelling of trace amounts of mont/tlorillonite on the permeability of the .samples. Most of the damage to the permeability when reservoir sands containing trace amounts of montmorillonite are exposed to fresh water is due to dispersion and movement of clays. Blockage of pores by the increased volume of expanded montmorillonite is believed to result in permeability damage that is small in comparison to the observed damage to the samples tested. INTRODUCTION Studies have shown that permeability is severely damaged when sands containing only small amounts of montmorillonite are contacted by fresh water.15 When samples of sands containing large amounts of montmorillonite are placed in fresh water in the laboratory, these samples may completely disintegrate, forming an unconsolidated mass of larger volume than that occupied by the dry sample." In this case, it is apparent that the swelling of montmoril-lonite has destroyed the pore structure of the sand. If only a trace of montmorillonite is present in a sand. samples may remain intact when saturated with water, although the permeability to water is a small fraction of the gas permeability of the dry sample. Many workers in the field of water sensitivity have attributed this reduction in permeability to the blocking of pores and reduction of pore size by the increased volume occupied by expanded mont- niorillonite. if the sand contains a detectable amount of montmorill'onite or mixed-layer clay containing rnontmorillonite. Logically3 the smaller amount of montmorillonite present in a sand, the smaller should he the effect of montnlorillonite swelling on permeability; however, the quantity of montmorillonite sufficient to cause severe damage by swelling is not known. Although hundreds of samples have been tested in our laboratory, no correlation has been established between the amount of montmorillonite in samples and the permeability reduction caused by fresh water. To many petroleum engineers, the phrase "clay swelling" is synonymous with "water sensitivity", or "permeability reduction" implying that any formation damage due to the hydration of clays is caused by swelling. Although all clays adsorb water on their surfaces, montmorillonite is the only clay mineral commonly found in reservoir rocks which adsorbs water between intercrystalline layers, resulting in expansion of the clay particle. As montmoril-lonite swells, the first few layers of water adsorbed between platelets are strongly held and well oriented, and the montmorillonite retains its crystalline structure, although expanded. As swelling of sodium montmorillonite continues, the platelets become farther apart and the forces orienting the platelets in the crystalline structure become weaker, resulting in a less orderly orientation of platelets. In an abundance of water, small groups of platelets may become detached from the original monl-rnorillonite particle and may be dispersed throughout the water phase. Because of its swelling properties, sodium montmorillonite is very easily dispersed in water. Particles of other clay minerals. such as illite and kaolinite may also be dispersed in water. causing water sensitivity of sands not containing montmorillonite. The presence of an immobile layer of water adsorbed on the surface of clays has been considered a possible cause of the low permeability to water of dirty sands. Grim states that the thickness of the layer of immobile water held by sodium montrnorillonite is three nlolecular layers or 7.5 A (angstroms), with some orientation of water extending to 100 A. Assuming a very thick, immobile water layer adsorbed on the surface of a pore represented by a capillary tube, the maximum effect of the water layer on permeability can be calculated. Using a pore radius of 10 ' cm and an immobile water layer of 50 A. the calculation shows the permeability to be reduced only 2 per cent. Similar calculations can be used to show that the effect of electro-osmotic counterflow is of the same order of magnitude as that of bound water. The reduction of the permeability to water by either an immobile water layer

Jan 1, 1966

By H. L. Shergold, O. Mellgren

Concentration of fine quartz particles at the iso-octane/water interface has been investigated under different conditions of pH and dodecylamine concentration. The results obtained from the related studies on the effect of amine concentration and pH on the interfacial tension, adsorption density, electrokinetic potential, contact angle, and concentration of the various amine species in the system are presented. A good correlation was obtained between these different variables. It is well-known that very fine mineral particles are difficult to float in conventional flotation machines. Flotation rate studies have revealed that the rate of flotation of fine mineral particles is much smaller than that of coarser size fractions. The theories accounting for this behavior have been discussed by Arbiter and Harris1 and also Meloy.2 Theoretically, a hydrophobic fine particle might never make contact with a bubble because of the presence of an energy barrier in the vicinity of the air/water interface.' This energy barrier will have electrostatic, hydrodynamic, and Van der Waals force components. It was thought that by using an oil phase instead of air the energy barrier would be decreased so that fine particles could be concentrated at the oil/water interface more readily than at the air/water interface. The technique used involves dispersing the fine particles in water, containing the appropriate chemical reagents, and injecting a fine dispersion of iso-octane oil droplets into the pulp. After vigorous conditioning, the pulp is passed into a separating column where the oil droplets coated with a layer of mineral particles rise to the surface to form a separate layer. Air is introduced into the base of the separating column to ensure that heavy agglomerates of oil and particles report with the organic layer. This technique has been described previously4 and adopted by Lai and Fuerstenau5 who studied the alumina-dodecyl sulfonate system. The interfacial phenomena in the system composed of hematite, water, and iso-octane in the presence of sodium dodecyl sulfate have been studied and the results reported" earlier. This paper describes the results obtained from investigations into the interfacial phenomena in the quartz/water/iso-octane system in the presence of dodecylamine. The technique used in measuring the interfacial tension, electrokinetic potential, contact angle, and adsorption density were similar to those described previously? Materials Selected pieces of a high purity natural quartz, from the Isle of Man, were crushed in a laboratory jaw crusher and pulverizer. The — 52+72 mesh size fraction was retained and leached with successive washes of hot concentrated hydrochloric acid to remove iron impurities. When no iron was detected in the solution by ammonium thiocyanate, the quartz was washed thoroughly with distilled water until the conductivity of the wash water assumed that of the distilled water. Samples of 25 g of the —52+72 mesh quartz were ground for 5.25 min in an agate vibratory mill. The ground product was 100% —44 m and 57% —10 am, as determined by the Andreasen pipette. The specific surface area of the sample used for the adsorption and flotation tests was 0.94 sq m g-l. This corresponds to a mean particle diameter of 2.4 am. The —44 am quartz sample was stored under vacuum in the presence of silica gel crystals. For the contact angle determination between the three phases, quartz, iso-octane, and water, a piece of the natural quartz was ground into a block about 15 mm long, 15 mm wide, and 5 mm thick. One surface of the block was then polished by successively finer grades of silicon carbide "paper." The final polishing was conducted with alumina on a "hyprocel" paper. The polished quartz specimen was cleaned using nitric acid and ethyl alcohol followed by a wash with distilled water and then stored under distilled water. This pro-

Jan 1, 1971

By M. W. BERNEWITZ

ALTHOUGH many persons know that a lot of type metal and etchings are used in the U. S. Government Printing Office few would expect to find anything on metals in the annual report of the Public Printer, George H. Carter. Yet the report for the fiscal year ended June 30, 1931, contains many interesting items. For example: Among the 57,500,000 lb. of materials and supplies delivered to the printing office was little new metal, but the metal in circulation is 6,000,000 to 7,000,000 lb. In the cost of production $31,523 is charged against metal, nearly one-third for salaries and wages. In miscellaneous sales were $4,696 from waste metal and $1,147 from waste gold (from books). Electrotype and stereotype covered 11,438,314 sq. in. The vaults and storage rooms contain 1,700,000 plates and 130,000 pages of type containing 4,600,000 lb. of metal valued at $275,000. In what was known as the Congressional Globe vault were 46,000 stereotype plates; these were salvaged by remelting for other platemaking service. The Congressional Record superseded the Congressional Globe in 1873.)

Jan 1, 1932