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By L. S. Darken, H. A. Wriedt

An investigation has been made of nitrogen absorption by the lattice defects in a low-carbon steel afte~ Plastic deformation. Specimens in which defects were distributed by various combinations of cold rolling and vacuum heat treatment were equilibrated with controlled ammonia + hydrogen mixtures at 300° to 450°C to study the relation between the solubility and the thermodynamic activity of nitrogen. The results are interpreted in terms of nitrogen being absorbed upon two different types of defect sites, called A sites and B sites. The concentrations of these sites are calculated for specimens with various histories of straining and annealing; and the thermodynamic relations descrihing the equilibrium distribution of nitrogen among the A, B, and ordinary interstitial sites in ferrite are evaluated as follows: THE generalization that the solute atoms in a solid solution interact with imperfections in the solvent lattice is now universally recognized and the subject of an extensive literature. All types of imperfections—point, line, or surface—exhibit these interactions, but the relative importance of each type depends upon its concentration, the strength of its interaction with the particular solute atom, and whether the interaction is attractive or repulsive. The strength and sign of the interaction vary with the vectorial displacement of the solute atom from the imperfection in the crystal. The concentration of lattice defects increases during plastic deformation and the effect of the imperfections upon the solute atoms is usually perceived only after cold work or irradiation. Two experimental methods have previously been used to observe the effects of interaction between nitrogen atoms and lattice imperfections in a iron. Internal friction, which was first used for this purpose by Dijkstra,1 has been applied more often than the electrical-resistivity method of Cottrell and Churchman.2 The method of the present investigation has not been used before.* Uniform specimens of steel with a metastable defect structure are produced by cold rolling and subsequent heat treatment below the recrystallization temperature. Variations in the defect structure are obtained by varying the amount of strain and the heat-treatment conditions. The specimens are then saturated with nitrogen at moderately elevated temperatures in ammonia + hydrogen mixtures having various thermodynamic activities of nitrogen below saturation with Fe4N. From the nitrogen contents of analyzed samples, the metastable equilibria of interactions between the defects and nitrogen can be established and the concentration of sites for nitrogen atoms in the lattice defects calculated. A steel was used in the present experiments instead of purified iron or iron alloys because the amount of nitrogen absorbed at defects is larger in the steel over a much wider range of experimental conditions and could therefore be measured more accurately. The effect of alloy composition is discussed in Part II of this paper; it is sufficient to say here that impurities and phase heterogeneity in ferritic alloys favor the generation and/or retention of larger defect concentrations during plastic deformation and annealing at 300° to 500°C. MATERIALS AND EXPERIMENTAL PROCEDURE The experimental specimens were prepared from stock of a low-carbon steel, which will be called "X steel" here, with the composition: C, 0.12 pct; Mn, 0.43 pct; P, 0.010 pct; S, 0.034 pct; Si, 0.007 pct; As, 0.086 pct; Cu, 0.022 pct; Ni, 0.009 pct; Cr, 0.003 pct. The stock was all from a single ingot made by the basic open-hearth process, which was hot-rolled to strip 0.080 in. thick.. This hot-rolled strip, given the code designation "XH", was the starting material for preparing a series of cold-rolled sheets. The latter are designated "XC27",

Jan 1, 1965

By D. de Fontaine

A convolution procedure is described for obtaining an analytical expression for the composition profiles of solute concentration:; in binary solid solutions. The free energy of solutions containing such compositional inhomogeneities can then be evaluated and the stability of spherically symmetric clusters (G.P. zones, for short) us a function of their radii and central compositions can be studied accordingly. Two characteristic zone radii are defined: the minimum radius (RM) corresponding to the smallest zone for which growth is energetically favored over dissolution, and the critical radius RK) corresponding to zones associated with the minimum work of formation. The values of RM and RK coincide at the two classical limits of nucleation and growth and spinodal decomposition. As the spinodal is approached, however, RM and RK diverge increasingly and it is proposed that the initial] decomposition morphology is governed more closely by the minimum, rather than by the critical radius since the former possesses no singularity within the m eta stable phase boundary. Reversion is briefly discussed in the light of the foregoing and it is shown that a set of reversion temperatures located between the coherent miscibility gap and the coherent spinodal must correspond to a given distribution of low temperature zones. SINCE the early works of Guinier1 and preston,2 the kinetics and morphology of GP zones have been studied extensively, see Ref. 3, for example, for a recent review. Nevertheless, a completely satisfying theoretical treatment of the decomposition of meta-stable or unstable binary solid solutions is still lacking due to the almost unsurmountable mathematical difficulties that one encounters in attempting to solve the pertinent diffusion equation which, in principle, describes the whole process. This equation, first derived by Cahn for the initial stages of spinodal decomposition,4 is a nonlinear partial differential equation of the fourth order in anisotropic space, a general analytical solution of which is completely out of the question. From this equation, some prediction can be made, however, concerning the later stages of spinodal decomposition5 and a recent numerical solution6 of the equation in the case of one- and two-dimensional composition modulations of a solid solution inside the spinodal has led to the following considerations: the sinusoidal morphology7 is to be expected only for solutions of average composition c, located near the center of the coherent miscibility gap.8 For solutions with co closer to the spinodal decomposition, depleted shell zones9 should constitute the first recognizable decomposition product, later evolving to iso- lated, enriched preprecipitates in a uniformly depleted matrix as this must, in all cases, constitute the final metastable morphology, barring, of course, loss of coherency and change in crystal structure. In agreement with the qualitative description of Bonfiglioli and Guinier,l0 it thus appears that the various models discussed by previous authors are, in fact, idealized successive stages of the general decomposition process. Unfortunately, corresponding calculations for a solid solution outside the spinodal are not yet available because of two additional difficulties: it is essential that the diffusion equation be solved in three-dimensional space, and furthermore, one must include in the equation an appropriate "source term" describing the statistics of the creation of composition fluctuations required to trigger the nucleation events. At present, a general treatment of this problem does not appear to be tractable. Nevertheless, by using a modelistic approach, i.e., by selecting a priori certain composition variation profiles and by evaluating their associated free energies, one can draw certain conclusions relative to the stability of these isolated composition modulations or "zones", both outside and inside the spinodal. This is the object of the present investigation. THEORY We shall now describe a standard four-parameter spherically symmetric GP zone, evaluate its free energy according to the Cahn and Hilliard11 formula (Eq. [5], below), and plot the corresponding energy surfaces as a function of zone amplitude and radius as

Jan 1, 1970

By J. O. Brittain, E. Lautenschlager

Yield point measurements were made on polycrys-talline specimens of a iron deformed various amounts at 770, 1950, or 273°K, aged, and redeformed at 77: 195°, or 273°K. When the prestrain temperature is lower than that subsequent to aging, the yield point return is suppressed relative to specimens deformed at the same temperature both before and after aging. The degree of suppression is a function of both the magnitude of prestrain at the lower temperature and the difference between the deformation temperatures before and after aging. It is proposed that the suppression is caused by the formation of dislocation barriers during the initial low-temperature deformation. The aging kinetics of polycrystalline a-iron wires deformed at 77o or 303oK were studied at 44 " and 64 "C using internal friction measurements. No change was noted as a result of the difference in prestrain temperature. IN an earlier investigation1 it was observed that the return of the yield point was suppressed when a poly-crystalline specimen of a iron was plastically deformed at 77oK, aged at room temperature, and subsequently tested at room temperature. In order to investigate this observation, a research program was undertaken to measure the effect of prestrain temperature on the strain aging of a iron.' According to Thomas and Leak,3 return of the yield point and internal friction are similar measures of strain aging since both are dependent on solute atoms leaving the solid solution. The decrease in internal friction as a function of aging time is indicative of the removal of solute atoms from the solution, while the return of the yield point as a function of aging time gives the rate of arrival of solute atoms at the dislocations. According to Cottrell and Bilby,4 the solute atoms create an "atmosphere" which locks the dislocations and causes a return of the yield point upon restraining. In this experiment, both methods of measuring strain aging were employed in order to have two independent measurements of the strain aging phenomenon. In a previous study,5 the strain aging kinetics of a similar lot of a iron were measured for specimens which were prestrained and tested at the same temperature over the range of 77" to 273°K. Although some differences were found in the correlation of the two methods employed for measuring strain aging, the kinetics of strain aging were unaffected by the change of prestrain and test temperature. In another study,6 dislocation line tension and the density of the solute atmosphere were found to contribute to the return of the yield point when ingot iron specimens were prestrained at 303°K and tested at a lower temperature, namely 77°K. This paper is concerned with changes in strain aging kinetics produced by pre-straining at 77" to 303°K and testing at either the prestrain temperature or at higher temperatures up to 273°K. EXPERIMENTAL PROCEDURE The polycrystalline a iron specimens used in both the tensile and internal friction tests were 0.033-in. diam ingot iron wires, wet hydrogen treated and re-carburized. A more detailed procedure for processing a 3/16 in. ingot iron rod (nominal wt. pet composition: Fe - 0.013; C - 0.0125; Mn - 0.023; Si -0.005; P - 0.0023; S - 0.11; Cu - 0.004 N) to 0.033 in. diam specimens containing approximately 0.020 wt pet C and no detectable nitrogen with a grain diameter of 0.033 to 0.040 mm is given elsewhere.5 Immediately prior to testing, specimens were solution treated for 15 min at 700o ± 2°C in a static vacuum of less than 50 ?. of Hg and rapidly quenched into an ice-water bath while still enclosed in a 3 mm quartz vial. The internal friction specimens had 8-in. gage lengths and the tensile specimens had 2-in. gage lengths. The wires used as tensile specimens were first run as internal

Jan 1, 1962

By H. Wilton Clark

VARYING in thickness and in number from place to place, coal seams in the Canadian Rockies also range in pitch from nearly horizontal to vertical, sometimes with overturns. Over the entire coal-bearing area there are considerable differences of rank in coals of the same geological age, and there are marked differences in ash content and wash-ability characteristics. Correlation of seams at mining operations within a few miles of each other has often proved impossible. These factors influence mining methods, and, of course, production results. The oldest coal formations of western Canada are of Lower Cretaceous age, as the carboniferous sediments are marine and contain no coal. Coal is also present in formations of Upper Cretaceous and Tertiary ages. The rank of coal varies from semi-anthracite in some operations in the Kootenay and Luscar formations of the Lower Cretaceous in the Rockies to lignite in the Tertiary fields of the Saskatchewan prairies. Fig. 1 shows the general extent of the formations. The pitching seams, chiefly Lower Cretaceous, occur in the western belt of the Rocky Mountain foothills and the eastern slopes of the Rockies themselves. (The road to Tent Mt. strip pit, elevation 7000 ft, is shown on p. 832.) Formations extend from the U. S.-Canadian boundary for several bundred miles in Alberta and continue for a similar distance in British Columbia. Present geological estimates show a probable reserve of the order of 25,000 million tons of coal ranging from high volatile bituminous to semi-anthracite, with a large percentage of coking coal, constituting one of the major world reserves of that type. It should be noted that although the quoted estimate probably errs on the conservative side, the question of access to the seams in a mountainous terrain will always be a problem; a wide divergence may exist between actual reserves and the quantities of coal economically recoverable. An excerpt from the Canadian government Report of the Royal Commission on Coal 1946 states that conditions favorable to coal formation were intermittent and these intervals relatively brief in comparison with periods in which no coal was formed. Conditions were favorable to the growth or accumulation of vegetation in one area, while fresh water sediments and marine shales were being deposited in other areas. During periods of emergence the coal deposits were subjected to erosion or were covered by coarse sands and gravels from the mountains, whereas during submergence they were covered by fine clays deposited in embayments of the sea. During some of the periods of coal formation, volcanic activity deposited beds of fine volcanic ash and dust with the coal-forming vegetation. Coal deposits reach their greatest development in the mountains and thin rapidly to the east into the plains area, where they are deeply buried beneath younger sediments. For example, in the Fernie area of southeastern British Columbia there are in places 22 seams having an aggregate thickness of 150 ft in a stratigraphic interval of 3500 ft, whereas at Cole-man in the Alberta Crowsnest area the measures are only 800 ft in thickness and contain a maximum of five seams aggregating about 47 ft of coal. At Belle-vue, 10 miles further east, the measures are reduced to 430 ft with only three seams aggregating about 37 ft of coal. Subsequently the tremendous forces involved in the upthrust of the Rocky Mountains produced great displacement of the coal-bearing formations and at the same time a change in geologically young coals from low to high rank. The floor or footwall of most seams consists of carbonaceous shales, which are almost as adaptable to bending as the coal seams themselves. The seams show very few cleats or cleavage planes and have been so weakened structurally that as mined 50 pct or more will pass through a ¼-in. screen, seldom

Jan 1, 1955

By J. Nutting, D. H. Kirkwood

The oxidation of lead sulfide in air between 200° and 350°C has been investigated by electron diffraction from thick sulfide films and from galena surfnces. It has been demonstrated that sulfate is the stable reaction product up to 570°C. Sulfate is HAGIHARA has investigated' single crystals of galena roasted in air by the reflection electron-diffraction technique, which owing to the very limited penetration of the beam into the crystal gives information of the nature of the surface only. He has shown that up to 280°C the first oxidation product is lead sulfate, followed by lead mono-oxysulfate (PbO . PbS04). At longer times and higher temperatures more complex patterns appeared which could not be analyzed. All of these patterns were of streaks or spots arising from crystals oriented on the galena surface, and it is probable that these crystals are lead compounds whose structures have not been determined, such as the other oxysulfates (2Pb0 • PbS04 and 4Pb0 . PbS04) or a number of oxides. Certain lead sulfide films, formed chemically, give ring patterns in transmission electron diffraction2 because they are polycrystalline, and should also give ring patterns of the products after oxidation. It was thought that a diffraction study would reveal the sequence of phases produced in the reactions at different temperatures, since X-ray powder patterns are available for many lead compounds. PREPARATION OF FILMS The films were prepared by passing H2S over a saturated solution of lead nitrate in water. Once a silvery film had formed on the solution surface, no further thickening was apparent. The films were transferred by a gauze to a bath of distilled water for washing and pieces of film were caught on small discs on which they were dried. The discs were formed initially on galena up to temperatures of 300°C, followed by oxide and oxysulfates in turn at longer times. The appearance of- these phases is believed to result from an inadequate rate of supply of sulfur to the top surface 01. the crystal. standard Siemens mounts, made of platinum alloy, and had seven 20-p apertures drilled through them. The parts of the film which had dried onto the disc surface were light blue in color, which is the interference color of a film about 600A in thickness. A strong pattern of lead sulfide was obtained in transmission electron diffraction through the apertures but slight broadening indicated a crystallite size of around 200A. Tilting a sulfide film in the beam produced arcing of the rings, increasing the intensities of the (Ill), (3111, and (222) rings and reducing (200) and (220). This arises from preferred orientation in the film, a [loo] direction of the crystallites being normal to the plane of the film. These specimens were oxidized in an oven maintained at the required temperature. The reported times include that taken to heat the film to the reaction temperature. STABLE PHASES FORMED IN OXIDATION The conditions in which various oxidation products of lead sulfide are stable have been considered by the authors in a previous paper.3 It was shown that in a normal atmosphere, taken as containing lo-' atm of SOs, lead sulfate would be stable up lo about 570°C. This was confirmed by oxidizing thin films of sulfide for several days, and the analysis of the transmission-diffraction pattern is given in Table 1. The fit with the patt$rn from X-rays is good, except for the missing 3.62A ring. Some disagreement in intensities of reflections given by X-rays and electrons is to be expected. Up to 570°C a spotty pattern of sulfate was still obtained, indicating grain growth, but above this temperature the film disintegrated. Probably this is associated with the decomposition to PbO . PbS04. It needs to be emphasized that the atmosphere

Jan 1, 1965

By Larry Kaufman

A useful method for estimating the entropy of NaCl type compounds has been developed by combining the Debye theory of specific heat with the Lindemann formula. This method pemnits calculation of the entropy from a knowledge of the atomic weight, atomic volume, and melting point of the compound. Comparison of the calculated and observed entropies of 35 NaCl type compounds over a wide temperature range yields good agreement thus establishing the usefulness of the method. Application of the method to other crystal types is also discussed. KUBASCHEWSKI~ has suggested a useful method of estimating the enthalpy of formation of inter-metallic compounds from a knowledge of the crystal structure, lattice parameter, and heats of sublimation of the component elements. This method is quite valuable in predicting the tendency for compound formation in a given system and is of particular value in considering systems for which no experimental data are available. In order to supplement the enthalpy calculation afforded by Kubschewski's method, it would be of value to be able to estimate the entropy of compounds so that the entropy and free energy of formation could be evaluated. Although a considerable body of such data determined by calorimetric and equilibration techniques exists at present, the difficulty of making such measurements (particularly at high temperatures) and the ever increasing number of new compounds which are of interest make the desirability of such a computational method clear. This paper deals with a method for calculating the entropy of a compound from a knowledge of the atomic weight, atomic volume, and melting point. Since these data are generally easier to determine and therefore more readily available than thermo-dynamic data, they should provide an additional tool in estimating the stability and reactivity of compounds at high temperatures. I) THE ENTROPY OF PURE METALS As a first approximation, the specific heat of a pure metal can be represented by a sum of terms where C,($/tI is the vibrational specific heat calculated on the basis of the Debye theory, lo4 TC, (0/T) is an approximation to the Cp - C, correction. T is the electronic specific heat, and Cp (p) is the magnetic specific heat. Although the Debye theory does not provide a complete description of the vibrational specific heat, i.e., the Debye temperature 0 is not a constant, it does provide a good approximation when used properly. Blackman6'7 has written several reviews on this subject discussing the different values of 0 determined by various methods (specific heat, X-rays, elastic constants, electrical resistivity, and so forth), as well as the observed temperature dependence of 0 with T. In the present case the 0 in Eq. [I] naturally refers to the specific heat 0. The variation of Debye 0 (as determined from specific heat measurements) with temperature is observed to exhibit its most radical behavior at very low temperatures. At higher temperatures the 8 values are observed to become more nearly constant. Blackman6'7 has presented the variation of 0 with temperature for several metals. His tabulation is reproduced in Table I. Reference to Table I shows that above a certain temperature level, 0 remains fairly constant. The value of 0 which is most useful in computing the specific heat, and hence the entropy, is the value of 0 in the range 0/6 « T « 0. In 1910, Lindemann' suggested a relation for estimating Debye 0 values. According to this formula, where V is the atomic volume, T is the melting point in 'K, M is the atomic weight, and CL is a constant. Mott and Jones9 present this formula and state that there is at present no satisfactory theoretical explanation, but that it does have an empirical basis. By using the valuesof 0 in Table I along with known1' values of M, T, and the molar volume VM, where the Lindemann constant can be evaluated. This

Jan 1, 1962

By W. A. White

UNDERCLAY squeeze is the plastic flowing of underclay below coal pillars into mined-out entries and rooms. Squeezes may be caused either by wet mine conditions where the moisture is taken up by the clay—making it more plastic—or by the presence of certain clay minerals, such as mont-morillonite, which are plastic when there is enough natural moisture. Under either condition, sufficient stress will cause the underclay to flow. Squeezes may fill an entry or room within several hours, or it may be several months before movement stops. Squeeze areas commonly cover hundreds or thousands of square yards. The Coal Div. of the Illinois State Geological Survey has collected samples of underclays from various mines and from cores drilled by coal companies in the state. From these samples natural moisture content, particle size and particle size distribution, and clay mineralogy are determined. Data from samples collected from the underclay below Herrin (No. 6) coal in the Lumaghi Coal Co. mine near Collinsville, Ill., are used in this report to clarify points in the discussion. Data from samples taken from other mines lead to the same conclusions. A generalized geological section for the area is given in Table I. The underclay below coal No. 6 ranges from a few inches to 3 or 4 ft thick. The upper 6 to 18 in. are noncalcareous; the lower part becomes more calcareous with depth. Limestone nodules become larger with depth, almost grading into the limestone below. In areas where the clay is nearly absent the limestone may thicken to take its place; thus they may complement each other in thickness. There are two types of squeeze areas in a mine. In one type up to 3 or 4 ft of underclay lie in what appears to be a depression in the limestone underneath. This is suggested by a rim surrounding the squeeze area where the underclay is thin and the limestone lies within a few inches of the coal. In the second type the underclay of the squeeze area is surrounded by underclay of similar thicknesses which does not squeeze. Test Methods: Natural moisture content, particle size and particle size distribution, and clay mineralogy were determined by the following methods: Natural moisture is the moisture content a clay contains in its natural environment, expressed in percentage of the weight of ovendried clay (110°C or 230°F). To obtain the natural moisture content, given in Table 11, the clay samples were sealed in containers as soon as the samples were taken in the mines. Particle size and particle size distribution were determined by the pipette method,' and the data were plotted as cumulative curves, Fig. 1, on semi-logarithmic paper. Particle size was plotted on the logarithmic scale and percentage on the arithmetic scale. The quartiles (diameters that correspond to frequencies of 25 and 75 pct) and medians (diameters that correspond to the frequency of 50 pct) of the samples were determined from these curves. The clay minerals were identified from the data obtained by differential thermal' and X-ray powder" techniques. The differential thermal analyses were made on the whole samples, whereas the X-ray analyses were made on fractions of less than 2p. Data and Discussion Moisture Content: After the sealed jars had stood for 24 hr, those that contained squeeze samples had perspired, so that droplets of water had accumulated on the insides of the jars. Table II shows the moisture in the clay after it had perspired for 24 hr. (This perspiring was not noted in samples from nonsqueeze areas.) After perspiration one of the squeeze samples still had a higher moisture content than the samples that did not squeeze. Clay Mineralogy: The thermal analysis, Figs. 2 and 3, indicates that the clay minerals are chiefly micaceous in type; the low-temperature endothermal

Jan 1, 1957

By Leonard R. Weisberg

The general properties of diffusion in GaAs are reviewed. A total of .fourteen atoms have been studied to date, and activation energies for eleven reported are (in ev): Ga (5.6), As (lo), Zn (2.49), Cd (2.43), Sn (2.5). Mn (2.75). S (4.0). Se (4.2). Ag (0.33), Cu (0.52). and Li (1.0). The dijfusion of the first eight atoms, as measured by Goldstein using radiotracer techniques, established the principle of sub lattice diffusion for both host and impurity atoms, since atoms substituting for gallium have lower activation energies than those substituting for arsenic. The diffusion constant of interstitial copper has been determined for the first time by Hall and Racette using heavily doped p-type samples in which interstitial copper predominates. The anomalous behavior of zinc, which has an abrupt diffusion front and a strong dependence on zinc concentration, has recently been quantitatively explained in terms of an interstitial-substi-tutional equilibrium-diffusion mechanism. Lithium and silver diffuse mainly interstitially, while the diffusion of phosphorus is complicated by the continual formation ofGap. Junction-migration measurements indicate diiferent results than radiotracer techniques, and this is one problem that still remains, together with discrepancies in cadmium-diffusion results, and an unexplained dependence of impurity diffusion on arsenic pressure. BESIDES the usual insights into the behavior of atoms in solids, studies of diffusion in semiconductors have additional importance for device applications. In fact, the amount of diffusion studies performed on a semiconductor might serve as a simple barometer of its technological importance. Thus, the information accumulated for GaAs is not yet quite comparable to that for germanium or silicon, but considerable knowledge is available. The diffusion of at least fourteen atoms has been investigated for GaAs, and the diffusion constants have been determined for eleven of these. Interesting results were found for GaAs that elucidated problems not previously solved for germanium or silicon. For example, the interstitial-diffusion constant for the very fast diffusant, copper, was first measured in GaAs. Also, solutions for interstitial-substitu-tional equilibrium diffusion in extrinsic material were provided first for GaAs, although they are ap- plicable to germanium, silicon, and other semiconductors. Studies in GaAs firmly established the concept of sublattice diffusion, which should have application in many different compound systems. The purpose of this paper is to review briefly the general state of knowledge concerning diffusion in GaAs. First some general aspects of diffusion will be covered, and next attention will be given to the results mentioned above. Diffusion in GaAs has been measured both by radiotracer and junction-penetration techniques, and some discussion will be given of differences in the two sets of results. The comprehensive work of oldsteinl-' has served as the primary reference for the diffusion of well-behaved substitutional atoms in GaAs. Since a review has recently been presented of many of these reults, details of the diffusion data will not be repeated. Neither will any discussion be given of the experimental techniques of diffusion measurements, except to note here, in passing, the simplicity and effectiveness of the precision lapping device employed by Goldstein.' I) EXPERIMENTAL RESULTS AND DISCUSSION A) Summary of Experimental Results. Diffusion constants D = Do exp(E/kT) have been determined for eleven atoms in GaAs: a,' AS,' n,'" Cd,'" n,' n,8 s, e,' Ag,O CU," and i." These results are summarized in Table I. In addition, diffusion was investigated for phosphorus,4'12 germanium,I3 and ilicon,' but Do and E were not determined. Radiotracer techniques were used for most of the studies except for lithium, where a combination of chemical and electrical techniques was employed, and germanium and silicon, where junction-migration techniques were applied. The diffusion of zinc, manganese, sulfur, and tin was also measured using junction migration.13'14 Goldstein demon-

Jan 1, 1964

By Nicholas J. Grant, Rolf Nordheim, Thomas B. King

Constant-load creep-rupture tests were conducted in an argon atmosphere at temperatures of 1600 to 2200°F on two heats of iron containing about 0.06 and 0.09 pct P in solid solution. The tests were conducted in the as-cast condition. Stresses were selected to give strain rates approaching those encountered in the hot working of steel, and within the limits of the creep-rupture test apparatus, namely. from about 0.001 to 50 pct per sec. FOR generations, rolling and forging practices have been developed largely by empirical methods, based on prior experience. While largely successful, difficulties are frequently encountered when new or different alloy compositions are tried for the first time. There is need to know the relationships which exist among temperature, strain rate, composition, and other variables on the deformation and fracture characteristics of steels. It has been shown for aluminum and several high-temperature alloys that the deformation and fracture characteristics follow rather well-defined laws and patterns which are closely related to the effects of strain rate, temperature, and composition.1"3 As the melting temperature of aluminum or its alloys was approached, it was possible to study the interplay of work-hardening factors and recovery or recrystal-lization, the latter resulting in improved ductility and increased resistance to intercrystalline fracture. In particular, the effects of composition are very poorly known. Within the meaning of "composition" should be included impurity elements, such as sulfur, phosphorous, lead, copper, and many others, as well as those elements which are added for alloying purposes in iron. The role of multiphase structures, in contrast to solid solutions, should also be studied in much greater detail. high strain rate creep-rupture tests would provide information regarding the deformation and fracture characteristics of metals at hot-working temperatures. It was also desired to establish the stresses which are necessary to accomplish the desired deformation, and to relate these to the strain rate and temperature. Secondly, it was the purpose of this particular study to determine the effects of phosphorus, within solid solution limits, on the deformation and fracture characteristics of iron at hot-working temperatures. EXPERIMENTAL PROCEDURE Two phosphorus levels were selected, one corresponding to the upper limit normally found for commercial steels, and one substantially higher than this, but within the region of solid solubility at the test temperatures chosen for this investigation. Twenty-pound heats were prepared by induction melting electrolytic iron in air in a magnesia lined furnace. After deoxidation with about 0.2 pct Al, ferro-phosphorus was added, and the heats were then poured into prefired silica molds. The purpose of using silica molds was to obtain a slow cooling rate during solidification to produce a relatively coarse grain size, producing a structure subject to some segregation and therefore more nearly characteristic of ingot structures. The major part of the casting assembly provided a large shrinkage head in order to produce sound castings and to promote slow cooling of the specimens. The primary austenitic grain size varied from ASTM No. 2 to No. 00. The composition of the heats, including a low phorphorus melt, used for comparison purposes, is shown in Table I. It will be noted that the oxygen content of the phosphorus containing heats is relatively high, in spite of the deoxidation practice, a condition which is difficult to control in small melts. Creep-rupture tests were nevertheless undertaken when it was noted that this quantity of oxygen did not appear to give results any different from those from a heat containing 0.01 pct 0, low phosphorus and comparable carbon Content;4 see Table 11.

Jan 1, 1961

By George W. Crawford, W. P. Aycock, E. W. Hough

Forty oilfield brines have been examined so far by a polarographic technique new in petroleum engineering called the "tensatnmetric method" by the team of biochemists who perfected its use in their field. Samples of brine were obtained from various oil fields in which the wells were known to be producing fluid from oil productive zones in well-known geologic formations. Most of the reservoirs from which the samples were obtained are believed to have an active water drive under the prevailing conditions of operation. The 40 samples represent brines produced front 16 different formations of various geologic ages. Graphs have been prepared of the data obtained in the testing of each sample, and the distinctive waife-like curves so obtained are characterized by reproducible profiles, called "response curves." Careful comparison of the response curves of salt water coming from different fields producing from the same geologic formation reveals that the curves are similar. The response curves of salt water coming from productive zones of different geologic formations are characteristically different. Preliminary work offers the further hope that response curves of an oilfield brine indigenous to a particular oil-bearing formation and hence representative of a particular geologic environment, such as deposit-ional and all subsequent morphological conditions, may be of value in reservoir engineering in the interpretation of surface and interfacial phenomena. For example, the wettability of the rock matrix and more specifically, the classification of productive oil-bearing strata as hydrophyllic or hydrophobic may be determinable. However, many more brines must be examined and the resulting response curves analyzed in comparison to known causal phenornena before this objective is achieved. INTRODUCTION One of the perennial moot questions in the literature of petroleum engineering is whether the reservoir rock is oil- or water-wet. Possibly an answer to this question could come from a careful examination of oilfield brines. None of the conventional methods of examining brines (chemical analysis, pH and electrical conductivity measurements, and the like) answer the question. Careful analysis of reservoir behavior observed in the exploitation of oil fields, particularly in the application of fluid injection, has been fruitful to the extent that a few reservoirs are believed to be properly classified. Physical chemistry suggests the behavior of reservoir brine and rock may be due to something in the brine in small amount. The ever increasing development and modification of theory in the general field of surface and interfacial chemistry has, and is, contributing to a better understanding of the problem, particularly as theory is verified by data. The work herein reported was begun in 1953 by Hough and Roebuck 1,2 who employed a new form of alternating current polarography, i.e., tensammetry, developed by Breyer, et a13,4 and who studied eight oilfield brines in adapting tensammetry to petroleum engineering needs. THEORY AND DEFINITIONS Tensammetry is a new technique of inquiry into surface phenomena. Specifically, a weak alternating current voltage is superimposed upon the direct current voltage applied to a dropping mercury electrode in contact with an electrolyte containing a small amount of a surfactant. The resultant alternating current can be measured and provides the experimental data for this new area of research. Under the influence of the direct current voltage, polar molecules arrange themselves in a double layer at the electrode. This double layer may be compared to a variable condenser, the capacitance of which is a function of the imposed direct current voltage. The direct current voltage determines the degree of adsorption of the surface active molecule on the electrode. Whenever the molecules are strongly adsorbed on the electrode, the capacitance of the double layer is low and the alternating current through the cell is low. Desorption occurs at some values of the direct current voltage, and at these voltages the capacitance of the double layer is high, resulting in an increase in the alternating current through the cell. The direct current

Jan 1, 1958

By C. S. Smith, Chih-Chung Wang

TURNBULL and his collaborators1,2 have developed the theory of homogeneous nucleation as applied, inter alia, to solidification of liquid metals. Vonnegut³ and Turnbull4 have shown that if a liquid metal is subdivided into small droplets a vast majority of them will undercool very considerably before solidification, generally to as low as about 0.8 of the freezing temperature on the absolute scale. The nuclei effective at small degrees of supercooling in bulk metal seem to be internal or surface heterogeneities, relatively small in number. If the metal is subdivided, those droplets that happen to contain such nuclei will solidify at a temperature not greatly below the true freezing point, but only a small part of the whole volume will be affected and the majority of the drops will under-cool to the much lower temperature at which homo- geneous nucleation occurs as a result of fluctuations. It occurred to one of the authors that an appropriate subdivision to give effective freedom from random nuclei is produced during the solidification of many alloys that contain a minor amount of a phase of low melting point, and that one might then expect marked undercooling of the distributed phase. Experimental: The alloys selected for initial study were copper with minor amounts of lead and bismuth, and aluminum with tin. In all these alloys, the major component freezes at a temperature not much below that of the pure metal, and there is little further change in constitution on cooling until the lower melting point constituent freezes in an almost pure state. Cooling curves were taken using the controlled heat flow method permitting approximate specific heats to be obtained. Chromel-alumel thermocouples were used, with the standard emf tables, since extreme precision was not needed. The crucible (3/4 in. id, 5/16 in. wall) was made of B & W K-20 insulating brick. It held about 10 cc of the alloy being investigated. The cooling rate was 2.5" to 2.9°C per min under a controlled temperature difference of 20°. Approximate specific heats were computed from the inverse rate curves together with data from a blank run and from a standard run with a copper cylinder of known heat capacity. The alloys for investigation were made from high-purity metals (99.99+pct) and cast into graphite molds. The castings were machined to fit the crucible and to provide a hole for the inner thermocouple. Cooling curves were taken after heating to a temperature about 50" above the melting point of the minor, lower melting-point, constituent. Results The lead phase in an alloy of copper with 5 pct lead did not undercool more than 3" below the melting point of lead (327°C) either as cast or after annealing to produce a new dispersion of the liquid phase. A copper-zinc-lead alloy with 23.75 pct zinc and 5 pct lead undercooled more but showed no thermal effect below 319°C. A cast alloy of copper with 5 pct bismuth undercooled to 249°C (M.P. bismuth 27l °C), but once solidification started it was completed at the same temperature. This was anticipated, since the bismuth forms a nearly continuous phase between the grains of copper, and a solid crystal nucleated anywhere would rapidly* con- sume the entire network of liquid, unless the physical continuity of the liquid were broken through volume changes, inadequate fluidity, or gas evolution. Similar arguments apply in the case of copper-lead alloys, where the lead-rich liquid forms a network along grain edges, though not grain faces. In both cases there would be a few isolated particles

Jan 1, 1951

By A. U. Seybolt, D. H. Haman

The rate of oxidation of the lowest nitride of chromium, Cr2N, was measured to be equal to the rate of oxidation of chromium metal. It was found that, while the presence of Cr2N in chromium does not affect the oxidation mechanism, a long exposure at high temperature affects the morphology of Cr2N in chromium, causing a massive internal nitriding along chromium pain boundaries. Marker expen' -ments showed that the rate of oxidation of Cr2N layers on chromium is determined by the rate of chromium diffusion through Cr,03. The rate of formation of Cr2N is determined by diffusion rate of nitrogen through Cr2N. This rate at 1000°C is around thirty times faster than the rate of oxiahtion. Evidence is presented which suggests that nitrogen from the air reaches the chromium through the Cr2O9 by migration through pores or cracks rather than by a diffusive process. IT has long been recognized that, when chromium or alloys containing substantial amounts of chromium are oxidized in air, some chromium nitride (Cr2N) is formed under the oxide scale. Although the presence of this nitride layer has often been described, there appears to have been no systematic study of the role played by the nitride during the oxidation process. Indeed, there have been conflicting re-ports'92 on the kinetics of oxidation of chromium and chromium alloys in air and in oxygen. However, it is now well-established'-5 that the rate-controlling process during the parabolic oxidation of chromium to Cr2O3 is chromium-ion diffusion through Cr2O3. Because of the importance of chromium-containing alloys as oxidation-resistant materials, it seemed desirable to investigate the behavior of chromium during oxidation with and without the presence of chromium nitride. Since a semicontinuous Cr2N layer forms relatively early during the oxidation of chromium in the air, chromium atoms must either pass out of or through the Cr2N layer to become incorporated in the growing Cr2O3 scale. Therefore, it seemed desirable to examine the oxidation behavior of the pure nitride. MATERIALS AND EXPERIMENTAL PROCEDURE The chromium used in this investigation consisted of slices of an ingot made from "five-nine" iodide chromium which had been argon-atmosphere melted in a Y2O 3-stabilized ZrO2 crucible in an induction furnace. The only impurity of any significance was 625 ppm of 0, which was usually reduced to a microscopically invisible amount by hydrogen annealing at 1400°C. However, one sample of chromium was used with the as-cast oxygen level as explained below. The samples were used after abrading through 600 Sic paper and then washing in toluene and alcohol. Both nitriding and oxidation experiments were performed in a vertical tube furnace connected to a glass vacuum system. 'This system was equipped with pressure measuring instruments for the range of 10 p to 1 atm, and a cartesian-diver pressure-control device was used in conjunction with a needle valve to allow control of pressure in the range of about 10 to 760 mm. The nitrogen or hydrogen gas was purified by passing through hot copper chips at 600°C, anhydrous calcium sulfate (Drierite), and liquid nitrogen. Oxygen gas was dried through the Drierite column and a dry-ice trap (-78°C). Changes in specimen weight were followed by a Pyrex helix used in conjunction with a cathetometer which could reproducibly be read to +0.001 cm, yielding an accuracy of about +0.2 mg. The spring was maintained in the cool upper part of the furnace tube where the temperature did not rise above about 35°C. The nitride in equilibrium with metallic chro-

Jan 1, 1964

WELL known member of the Institute, Henry Krumb, survived the Japanese earthquake and has written a most interesting description of his personal experience to a friend in New York, an extended excerpt from which we publish, by permission, below. Not having been written for publication it has increased value as a human document in its vivid description of personal impressions and sensations in the midst of such a catastrophe. The earthquake was the most terrible experience I have ever passed through. We arrived at Miyanoshita, Friday, Aug. 31, about 6 p.m., having left Yokohama about 2:30 that afternoon by automobile. It was a most beautiful ride, although rather warm, but not unusually so, as it has been uncomfortably hot ever since we arrived in Japan. The first part of this automobile trip was along the old highway from Kyoto to Tokyo, which is lined with fine old pine trees. There are 52 villages along this highway and we saw real Japanese country life: naked children, both boys and girls, and men wearing nothing but gee-strings. The country on either side was intensively cultivated, the green rice fields and lotus ponds making a most beautiful sight. The occasional hills were all re-forested with young pines. In places the road runs close to the ocean beaches. The last part of the trip was up a steep mountain road, cut out of the side of the mountain. On one side of the road, in the gulch below, was a roaring river. The road crosses this river several times. Miyanoshita is beautifully located on the side of a mountain about 400 ft. above this river at an altitude of 1400 ft. The grounds of the hotel are laid out in Japanese style, small lakes with fish, waterfalls and dwarf trees making a very pretty sight. On the morning of Sept. 1, after walking around the garden and the hotel, we went to our room and I started to write up a few notes. Mrs. Krumb was reading a guide book. A few minutes before noon she came over to the table where I was writing and said that it was about lunch time. Just at that moment hell broke loose. It was the first earthquake I have ever experienced and I did not immediately realize what was happening. The building was shaking as a mine office might shake when heavy blasting was going on near by. Mrs. Krumb, having experienced many earthquakes, stepped to the open door between our room and the bathroom and called to me to get out from under the chande-lier. The plaster was commencing to fall and a large wardrobe fell over. I then knew what was happening and ran to the win dow. Before I reached it a large chunk of plaster from the ceiling hit me on the head and cut my forehead and nose. Mrs. Krumb ran for the other window just as the marble mantelpiece and the dresser fell. Without any hesitation, she jumped out of the win-dow and I followed suit out of the other. Luckily neither of us sprained an ankle-we had jumped 8 ft. We started to runaway from the building but had not gone more than 25 ft. when a second shock or rather a continuation of the first became so violent and the ground under our feet was trembling so that it was almost impossible to stand up without holding on to a tree. The ground seemed to have become liquid and rocked violently, it seemed to me in a vertical direction. In some later shocks the movement was more horizontal. About this time Mrs. Krumb saw the blood on my face and commenced to break down, but only for a moment: As soon as she saw it was not serious she was all right and during the following days stood the experiences and hardships as well as the best of them:

Jan 11, 1923

By D. L. Everhart

The search for new deposits raises two important questions: Where did the metallic ions that formed the orebodies come from? What processes and geologic factors were involved in ore replacement? A review of the wide geological variety of recent uranium discoveries tells how these questions are being answered. SOONER or later intelligent exploration for uranium leads to these questions: Where did the metallic ions that formed the orebodies come from? What processes and geologic factors were involved in ore replacement? These matters, of course, make a big difference in how best to look for orebodies. Before these questions are discussed it might be well to point out other factors bearing on the subject. The whole business of uranium exploration is only a little over ten years old, participation by the public is only about six years old, and real interest and activity by more than a few large mining companies has arisen only in the past two or three years. Throughout this short period, uranium exploration has been affected by the unique influences of necessary security measures and by division of the overall job into individual projects by a large number of specialists in diverse fields. This has meant that a normal interchange of information on the nature of uranium deposits has really only just begun. Compared to the vast amount of published studies on iron, copper, lead, zinc, and gold deposits over the past 50 to 75 years, current knowledge of uranium deposits is in its infancy and much of the pertinent information is still scattered about in a number of unpublished sources. The volume of reports on all phases of uranium exploration is now beginning to mount at a remarkable rate, and geologists with widely varying specialized backgrounds in uranium geology are engaging in spirited debates over the origin of uranium and the relative importance of geologic controls of various deposits. One of the most interesting features of known uranium deposits of the world is the wide variation, see Table I, in character and geologic environment. It should be noted that many types became prominent during 1953. The davidite-bearing veins of Radium Hill, South Australia, are almost unique, although the same mineral occurs in a different kind of deposit in Mozambique. Recent studies indicate that brannerite disseminated in the granite near Cracker's Well, South Australia, may soon constitute uranium ore. Basalt has been added to the list of favorable host rocks in the Northern Territory of Australia. Basalt is also the host of the pitchblende veins of the Martin Lake deposit, Beaverlodge district, Saskatchewan. The truly remarkable rich and extensive Steen deposit near Moab, Utah, is of the uraninite-vanadium oxide type. Secondary hydrous uranium arsenates and phosphates constitute the uranium minerals in the disseminated deposits of the Wind River Basin, Wyo., a new district discovered in the summer of 1953. Uranium minerals in shales adjacent to fractures were newly reported in New Mexico and several other parts of the world during the year. The well-known important uraninite dissemination in the Rand conglomerates of South Africa has a counterpart, as discovered in the summer of 1953, in the Mississagi quartzite and conglomerate of the Blind River district, Ontario. Gunnar deposit of the Lake Athabaska district, Saskatchewan, consists of uraninite in both granite and sedimentary gneiss beneath a granite cap, and large new orebody of the Eldorado Co. in the same general area follows a preferred stratigraphic horizon in schists. Uranium is, generally speaking, a very soluble and ubiquitous element. It occurs in at least two valency states and for this reason is not easily tied down in natural solutions. As Gruner' has pointed out, it is probable that uranium starts in the hexava-lent state in nearly all solutions instrumental in its transfer. It is believed that under oxidizing conditions the uranium moves in solution as the uranyl ion, UO. In solutions ranging in pH from 1 to 5, the uranyl ion is most commonly in association with

Jan 1, 1955

By AIME AIME

FOUK fields of activity are now recognized by the A.I.M.E. in its award of medals for conspicuous achievement: the Saunders medal for mining, the Douglas medal for non- ferrous metallurgy the Lucai medal for petroleum, and the Rand medal for distinguished achievement in the broad field of mining administration including the organization and development of enterprises in all branches of the mineral industry. This last is known officially as the Charles F. Rand Memorial Medal, and it award is made possible through funds supplied by the Charles F. Rand Foundation. Until this year money thus available was used for other special projects, so that the forthcoming presentation of the Rand medal to Robert C. Stanley is notable as being the first time that achievement in mining administration has been thus recognized.

Jan 1, 1940

By AIME AIME

IN A STATEMENT summarizing general conditions in the Federated American Engineering Societies, the executive secretary, L. W. Wallace, expresses the belief that the Federation has made substantial progress. At the annual meeting of the American Engineering Council, to be held in Washington Jan. 5 and 6, this progress will be shown by reports covering activities in many fields. "Unquestionably," says Mr. Wallace, "the Federa¬tion has made favorable and permanent contacts in Washington. Through the, activities of Congress and of the new Federal administration. we have had the opportunity to render some really constructive service. We feel, however, that the great body of engineers are not adequately informed of the organization of the Federation, of its aims and purposes and of its activities.

Jan 1, 1921

By C. H. Mathewson

BERYLLIUM, magnesium, zinc and cadmium, together with mercury, constitute a coherent sub-group of the periodic system and these metals, excepting mercury; have been studied in sufficient detail by the new X-ray diffraction methods to prove their common adherence to the hexagonal close-packed type of crystal structure with a progressive increase in axial ratio as we pass through the group from beryllium to cadmium. The first four columns of Table 1 summarize the data on crystal structure of these metals reported in the International Critical Tables.1 The last two columns are based on results obtained in the present investigation. TABLE 1.-Lattice Constants and Twinning Law of the Be-Cd Group of Hexagonal Metals Dimensions of Unit Axial Cell, A Ratio Description of Twinning Element a° c° (c°/a°) Composition Axis Plane Beryllium 2.28(3) 3.60(7) 1.58 {1012} Probably 1 {1012} Magnesium 3.22 5.23 1.621 ,1 {1012} Zinc 2.65(7) 4.94(8 1.86(2) 11012 } 1 {1012) Cadmium 2.98 5.63 1.88(5) {1012} Probably 1 {1012} Twinning has often been observed in zinc and cadmium. The general aspects of this twinning are abundantly illustrated by photomicrographs, diagrams, etc., in the papers by Romig, and Mathewson and Phillips reported to this Institute in 1927.2. A determination of the composition

Jan 1, 1928

By Charles H. Fulton

FOR some time it has been thought that there should be > closer relationship between the members' of the Institute engaged in education in the mining schools, the mining, metallurgical, ceramic, and geological departments of universities, and the members of the Institute actually engaged in the production of mineral products and the operation and direction of works. The American Society of Chemical Engineers and the American Ceramic Society have for some years past devoted especial attention to the educational matters of their respective fields. The Engineering Foundation, representing the great engineering societies of the country, is deeply interested in technical education and maintains a Committee on Educational Research.

Jan 1, 1932

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 O. E. Kiessling

THE Committee-on Production Control, at its meeting held during the last annual session in February, 1930, evidenced great interest in problems of stabilization affecting all mineral industries. . No immediate program of activity for the Committee as a- unit was decided on, however,, and efforts during the past pear have consisted lirgely of further stressing the economic aspects of mineral production and of the action by committee members, :.serving in their individual capacities, in sponsoring constructive changes, in specific, industries. Of greatest interest to the general subject of production control in 1930 was the very definite advance toward better coordination of demand and supply in the petroleum industry. Furthermore, since opinion both within and without the oil industry now favors a constructive program, and with a gradual change in legal precedents, it seems not unreasonable to expect greater progress in the near future.

Jan 1, 1931